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(Physics) Chen F. F., Chang J. P. - Lecture Notes On Principles of Plasma Processing (Kluwer, 2002) PDF
(Physics) Chen F. F., Chang J. P. - Lecture Notes On Principles of Plasma Processing (Kluwer, 2002) PDF
PRINCIPLES OF
PLASMA PROCESSING
Francis F. Chen
Electrical Engineering Department
Jane P. Chang
Chemical Engineering Department
+ e
+
e-
ee-
e+
e-
+
e-
e-
e-
+ e
+
+
n+
n+
p+
p+
n
silicon
Plenum/Kluwer Publishers
2002
Preface
PREFACE
We want to make clear at the outset what this book
is NOT. It is not a polished, comprehensive textbook on
plasma processing, such as that by Lieberman and
Lichtenberg. Rather, it is an informal set of lecture notes
written for a nine-week course offered every two years at
UCLA. It is intended for seniors and graduate students,
especially chemical engineers, who have had no previous
exposure to plasma physics. A broad range of topics is
covered, but only a few can be discussed in enough depth
to give students a glimpse of forefront research. Since
plasmas seem strange to most chemical engineers,
plasma concepts are introduced as painlessly as possible.
Detailed proofs are omitted, and only the essential elements of plasma physics are given. One of these is the
concept of sheaths and quasineutrality. Sheaths are
dominant in plasma reactors, and it is important to develop a physical feel for their behavior.
Good textbooks do exist. Two of these, to which
we make page references in these notes for those who
want to dig deeper, are the following:
M.A. Lieberman and A.J. Lichtenberg, Principles of Plasma Discharges and Materials Processing (John Wiley, New York,
1994).
F.F. Chen, Introduction to Plasma Physics and Controlled Fusion,
Vol. 1, 2nd ed. (Plenum Press, 1984).
vi
accompanies the text has color figures that can be expanded for viewing on a computer monitor. There are
also sample homework problems and exam questions
there.
Table of Contents
TABLE OF CONTENTS
PREFACE
Plasma Physics
Plasma Chemistry
I. What is a plasma?
I. Plasma processing
99
100
I. Kinetic theory
103
125
ii
Table of Contents
PART A5: PLASMA SOURCES III
47
69
75
142
161
162
163
167
177
178
179
Table of Contents
XIII.
1.
2.
3.
4.
iii
PART B7: FEATURE EVOLUTION AND
MODELING
93
185
190
199
204
205
206
207
199
f(v)
f (v ) = Ae ( mv
A Maxwellian distribution
/ KT )
Part A1
energy an electron gets when it falls through an electric
potential of 1 volt, then we say that the temperature is 1
eV. Note that the average energy of a Maxwellian distribution is (3/2)KT, so a 1-eV plasma has average energy
1.5 eV per particle. The conversion factor between degrees and eV is
1eV = 11,600 K
Aurora borealis
Solar wind
Magnetospheres of earth and Jupiter
Solar corona and sunspots
Comet tails
Gaseous nebulae
Stellar interiors and atmospheres
Galactic arms
Quasars, pulsars, novas, and black holes
Plasma science began in the 1920s with experiments on gas discharges by such famous people as Irving
Langmuir. During World War II, plasma physicists were
called upon to invent microwave tubes to generate radar.
Plasma physics got it greatest impetus with the start of
research on controlled nuclear fusion in the 1950s. The
task is to reproduce on earth the thermonuclear reactions
used by stars to generate their energy. This can be done
only by containing a plasma of over 104 eV (108 K). If
this enterprise is successful, some say that it will be the
greatest achievement of man since the invention of fire,
because it will provide our civilization with an infinite
source of energy, using only the heavy hydrogen that
exists naturally in our oceans.
Another use of plasmas is in generation of coherent radiation: microwave tubes, gas lasers, free-electron
lasers, etc. Plasma-based particle accelerators are being
developed for high energy physics. Intense X-ray
3
sources using pulsed power technology simulate nuclear
weapons effects. The National Ignition Facility is being
built at Livermore for inertial confinement fusion. Femtosecond lasers can produce plasmas with such fast rise
times that very short chemical and biological events can
now be studied. Industrial plasmas, which are cooler,
higher pressure, and more complex than those in the applications listed above, are being used for hardening metals, such as airplane turbine blades and automobile parts,
for treating plastics for paint adhesion and reduced permeation, for nitriding surfaces against corrosion and
abrasion, for forming diamond coatings, and for many
other purposes. However, the application of plasma science that is increasingly affecting our everyday life is
that of semiconductor production. No fast computer chip
can be made without plasma processing, and the industry
has a large deficit of personnel trained in plasma science.
II. PLASMA FUNDAMENTALS
Plasma physics has a reputation of being very difficult to understand, and this is probably true when compared with fluid dynamics or electromagnetics in dielectric media. The reason is twofold. First, being a charged
fluid, a plasmas particles interact with one another not
just by collisions, but by long-range electric and magnetic fields. This is more complicated than treating the
charged particles one at a time, such as in an electron
beam, because the fields are modified by the plasma itself, and plasma particles can move to shield one another
from imposed electric fields. Second, most plasmas are
too tenuous and hot to be considered continuous fluids,
such as water (3 1022 cm-3) or air (3 1019 cm-3).
With particle densities of 109-13 cm-3, plasmas do not always behave like continuous fluids. The discrete nature
of the ions and electrons makes a difference; this kind of
detail is treated in the kinetic theory of plasmas. Fortunately, with a few exceptions, the fluid theory of plasmas
is all that is required to understand the behavior of lowtemperature industrial plasmas, and the quantum mechanical effects of semiconducting solids also do not
come into play.
Part A1
which create magnetic fields. Thus, the particle motions
and the electromagnetic fields have to be solved for in a
self-consistent way. One of Maxwells equations is Poissons equation:
D = E = e(ni ne ) .
(1)
(2)
(3)
2
eV
2 ( ne ni )e
=L
0 KTe
KTe
(4)
F KT I
=G
H n e JK
0
1/ 2
(5)
eV
L2 n
= 2 1 i .
KTe D ne
(6)
D = 7.4
Te (eV )
ne (1018 m 3 )
(7)
5
main body of the plasma, V would vary over a distance
depending on the size of the plasma. If we take L to be
of order 10 cm, an average dimension for a laboratory
plasma, the factor (L/D)2 is of order 108, so that ni must
be equal to ne within one part in 108 to keep the LHS reasonably small. In the interior of a plasma, then, the
charge densities must be very nearly equal, and we may
define a common density, called the plasma density n, to
be either ni or ne. However, there are regions, called
sheaths, where L is the order of D; there, the ratio ni /
ne does not have to be near unity.
The condition ni ne is called quasineutrality and
is probably the most important characteristic of a plasma.
Charged particles will always find a way to move to
shield out large potentials and maintain equal densities of
the positive and negative species. We have implicitly
assumed that the ions are singly charged. If the ions
have a charge Z, the condition of quasineutrality is simply ni = Zne. Note that one hardly ever has a whole cubic
meter of plasma, at least on the earth; consequently densities are often expressed in cm-3 rather than the MKS
unit m-3.
If L is of the order of the Debye length, then Eq.
(6) tells us that the quasineutrality condition can be violated. This is what happens near the walls around a
plasma and near objects, such as probes, inserted into the
plasma. Adjacent to the surface, a sheath of thickness
about 5D, forms, in which the ions outnumber the electrons, and a strong electric field is created. The potential
of the wall is negative relative to the plasma, so that
electrons are repelled by a Coulomb barrier. This is necessary because electrons move much faster than ions and
would escape from the plasma and leave it positively
charged (rather than quasineutral) unless they were repelled by this sheath drop. We see from Eq. (3) that
V(r) would have the right curvature only if ni > ne; that
is, if the sheath is ion-rich. Thus the plasma potential
tends to be positive relative to the walls or to any electrically isolated object, such as a large piece of dust or a
floating probe. Sheaths are important in industrial plasmas, and we shall study them in more detail later.
2. Plasma frequency and acoustic velocity
Waves are small, repetitive motions in a continuous medium. In air, we are accustomed to having sound
waves and electromagnetic (radio) waves. In water, we
have sound waves and, well, water waves. In a plasma,
we have electromagnetic waves and two kinds of sound
Part A1
waves, one for each charge species. Of course, if the
plasma is partially ionized, the neutrals can have their
own sound waves. The sound waves in the electron fluid
are called plasma waves or plasma oscillations. These
have a very high characteristic frequency, usually in the
microwave range. Imagine that a bunch of electrons are
displaced from their normal positions. They will leave
behind a bunch of positively charged ions, which will
draw the electrons back. In the absence of collisions, the
electrons will move back, overshoot their initial positions, and continue to oscillate back and forth. This motion is so fast that the ions cannot move on that time
scale and can be considered stationary. The oscillation
frequency, denoted by p, is given by
F ne I
G
H mJK
2
1/ 2
rad / sec
(8)
cs KTe / M
(9)
1/ 2
(10)
7
3. Larmor radius and cyclotron frequency
c =| qB | / m , or
e
rL
guiding center
(12)
The E B drift
In magnetic fields so strong that both ions and electrons have Larmor radii much smaller than the plasma
Part A1
radius, the particles guiding centers drift across B in response to applied electric fields E (the component perpendicular to B). This drift speed is given by
vE = E B / B 2 .
(13)
ne = ni = n
ns
ni
PRESHEATH
ne
PLASMA
SHEATH
xs
(14)
(15)
(16)
9
ni
1
=
ns
2 1/ 2
1 2eV / Mvs
(17)
(19)
+
-
PLASMA
SHEATH
2
SHEATH
1
(20)
10
Part A1
If a presheath has to exist, the density ns at the
sheath edge cannot be the same as the plasma density n
in the body of the plasma. Since the ions have a velocity
cs at the sheath edge, their energy Mcs2 is KTe, and
there must be a potential drop of at least KTe between
the body of the plasma and the sheath edge. Let us now
set V = 0 inside the main plasma, so that V = Vs at the
sheath edge. The electrons are still assumed to be in a
Maxwellian distribution:
ne = n0eeV / KTe .
(21)
Since the integral of an exponential is still an exponential, it is the property of a Maxwellian distribution that it
remains a Maxwellian at the same temperature when
placed in a retarding potential; only the density is
changed. There is only a small modification in the number of electrons moving back from the sheath due to the
few electrons that are lost through the Coulomb barrier.
Thus, Eq. (21) holds throughout the plasma, presheath,
and sheath, regardless of whether there are collisions or
not. If eVs = e|Vs| = KTe, then Eq. (21) tells us that
ns = n0e-1/2 = 0.6n0 n0 .
(22)
11
100.00
Argon Momentum Transfer Cross Section
Square angstroms
10.00
1.00
0.10
0.01
0.00
0.01
0.10
1.00
Electron energy (eV)
10.00
100.00
We consider first the collisions of ions and electrons with the neutral atoms in a partially ionized plasma;
collisions between charged particles are more complicated and will be treated later. Since neutral atoms have
no external electric field, ions and electrons do not feel
the presence of a neutral until they come within an
atomic radius of it. When an electron, say, collides with
a neutral, it will bounce off it most of the time as if it
were a billiard ball. We can then assign to the atom an
effective cross sectional area, or momentum transfer
cross section, which means that, on the average, an electron hitting such an area around the center of an atom
would have its (vector) momentum changed by a lot; a
lot being a change comparable to the size of the original
momentum. The cross section that an electron sees depends on its energy, so in general a cross section depends on the energy, or, on average, the temperature of
the bombarding particles. Atoms are about 108 cm (1
Angstrom) in radius, so atomic cross sections tend to be
around 1016 cm2 (1 2) in magnitude. People often express cross sections in units of a02 = 0.88 1016 cm2,
where a0 is the radius of the hydrogen atom.
At high energies, cross sections tend to decrease
with energy, varying as 1/v, where v is the velocity of the
incoming particle. This is because the electron goes past
the atom so fast that there is not enough time for the
electric field of the outermost electrons of the atom to
change the momentum of the passing particle. At low
energies, however, (v) can be more constant, or can
even go up with energy, depending on the details of how
the atomic fields are shaped. A famous case is the Ramsauer cross section, occurring for noble gases like argon,
which takes a deep dive around 1 eV. Electrons of such
low energies can almost pass through a Ramsauer atom
without knowing it is there.
12
Part A2
+
An ion-neutral charge exchange
collision
(3)
13
cross section for each such transition or each spectral line
that is characteristic of that atom. Electrons of higher
energy can knock an electron off the atom entirely, thus
ionizing it. As every freshman physics student knows, it
takes 13.6 eV to ionize a hydrogen atom; most other atoms have ionization thresholds slightly higher than this
value. The frequency of ionization is related by Eq. (3)
to the ionization cross section ion, which obviously is
zero below the threshold energy Eion. It increases rapidly
above Eion, then tapers off around 50 or 100 eV and then
decays at very high energies because the electrons zip by
so fast that their force on the bound electrons is felt only
for a very short time. Since only a small number of
electrons in the tail of a 4-eV distribution, say, have
enough energy to ionize, ion increases exponentially
with KTe up to temperatures of 100 eV or so.
Double ionizations are extremely rare in a single
collision, but a singly ionized atom can be ionized in another collision with an electron to become doubly ionized; for instance Ar+ Ar++. Industrial plasmas are
usually cool enough that almost all ions are only singly
charged. Some ions have an affinity for electrons and
can hold on to an extra one, becoming a negative ion.
Cl and the molecule SF6 are common examples. There
are electron attachment cross sections for this process,
which occurs at very low electron temperatures.
Debye cloud
A 90 electron-ion collision
14
Part A2
tial that can leak out of the Debye cloud is about KTe
(see the discussion of presheath in Sec. II-5). Because of
this shielding, incident particles suffer only a small
change in trajectory most of the time. However, there
are many such small-angle collisions, and their cumulative effect is to make the effective cross section larger.
This effect is difficult to calculate exactly, but fortunately
the details make little difference. The 90 cross section
is to be multiplied by a factor ln , where is the ratio
D/h. Since only the logarithm of enters, one does not
have to evaluate exactly; ln can be approximated
by 10 in almost all situations we shall encounter. The
resulting approximate formulas for the electron-ion and
electron-electron collision frequencies are, respectively,
3/2
ei 2.9 106 ncm ln / TeV
3/2
ee 58 106 ncm ln / TeV
.
(4)
m.
(6)
15
field case.
4. Transition between neutral- and ion-dominated
electron collisions
The behavior of a partially ionized plasma depends a great deal on the collisionality of the electrons.
From the discussion above, we can compute their collision rate against neutrals and ions. Collisions between
electrons themselves are not important here; these just
redistribute the energies of the electrons so that they remain in a Maxwellian distribution.
The collision rate between electrons and neutrals
is given by
en = nn < v > en ,
(7)
cm 3 .
(8)
(9)
We then have
1/
en (3.3 1013 ) p i(1016 ) i 6 107 TeV 2
1/
2 105 pmTorrTeV 2
(10)
16
Part A2
collision frequency is given by Eq. (4):
3/2
ei 2.9 105 n / TeV .
(11)
(12)
(13)
For instance, if p = 3 mTorr and KTe = 3 eV, the crossover density is ncrit = 1.9 1011 cm-3. Thus, High Density Plasma (HDP) sources operating in the high 1011 to
mid-1012 cm3 range are controlled by electron-ion collisions, while older low-density sources such as the RIE
operating in the 1010 to mid-1011 cm3 range are controlled by electron-neutral collisions. The worst case is
in between, when both types of collisions have to be
taken into account.
E
-
(15)
(16)
17
and similarly for ions. How do these E-fields get into the
plasma when there is Debye shielding? If one applies a
voltage to part of the wall or to an electrode inside the
plasma, electrons will move so as to shield it out, but because of the presheath effect a small electric field will
always leak out into the plasma. The presheath field can
be large only at high pressures. To apply larger E-fields,
one can use inductive coupling, in which a time-varying
magnetic field is imposed on the plasma by external antennas or coils, and this field induces an electric field by
Faradays Law. Electron currents in the plasma will still
try to shield out this induced field, but in a different way;
magnetic fields can reduce this shielding. We shall discuss this further under Plasma Sources.
The plasma density will usually be nonuniform,
being high in the middle and tapering off toward the
walls. Each species will diffuse toward the wall; more
specifically, toward regions of lower density. The diffusion velocity is proportional to the density gradient n,
and the constant of proportionality is the diffusion coefficient D:
n(r)
u = Dn / n, De = KTe / m en ,
n
Dan
(17)
Eambipolar
= Dn .
(18)
The sum of the fluxes toward the wall from mobility and diffusion is then
e = n e E De n
(19)
i = + n i E Di n
Note that the sign is different in the mobility term. Since
and D are larger for electrons than for ions, e will be
larger than i, and there will soon be a large charge imbalance. To stay quasi-neutral, an electric field will naturally arise so as to speed up the diffusion of ions and retard the diffusion of electrons. This field, called the ambipolar field, exists in the body of the plasma where the
collisions occur, not in the sheath. To calculate this field,
we set e = i and solve for E. Adding and subtracting
the equations in (19), we get
i + e 2a = n( i e )E ( Di + De )n
(20)
i e 0 = n( i + e )E ( Di De )n
18
Part A2
From these we can solve for the ambipolar flux a, obtaining
D + e Di
n Da n .
(21)
a = i e
i + e
We see that diffusion with the self-generated E-field,
called ambipolar diffusion, follows the usual diffusion
law, Eq. (18), but with an ambipolar diffusion coefficient
Da defined in Eq. (21). Since, from (15) and (17), and
D are related by
= eD / KT ,
(22)
and e is usually much greater than i, Da is well approximated by
T
T
Da e + 1 Di e Di ,
Ti
Ti
(23)
n
n
D||
1 + ( c / c )
KT
D|| =
,
m c
||
1 + ( c / c ) 2
e
|| =
m c
,
(24)
19
unity, we have the in-between case. If and KT are the
same, electrons have c/c values (M/m) times larger,
x
B and their Larmor radii are (M/m) times smaller than for
ions (a factor of 271 for argon). So in B-fields of 1001000 G, as one might have in processing machines, elec+
trons would be strongly magnetized, and ions perhaps
+
weakly magnetized or not magnetized at all. If c/c is
large, the 1 in Eq. (24) can be neglected, and we see
+
that D c, while D|| 1/c. Thus, collisions impede
+
diffusion along B but increases diffusion across B.
We now consider collisions between strongly
magnetized charged particles. It turns out that like-like
collisionsthat is, ion-ion or electron-electron collisions
Like-particles collisions do not cause do not produce any appreciable diffusion. That is bediffusion, because the orbits after the
cause the two colliding particles have a center of mass,
collision (dashed lines) have guiding
and all that happens in a collision is that the particles
centers that are simply rotated.
shift around relative to the center of mass. The center of
mass itself doesnt go anywhere. This is the reason we
did not need to give the ion-ion collision frequency ii.
However, when an electron and an ion collide with each
other, both their gyration centers move in the same dix
The reason for this can
B rection. two particles gyrate in be traced back to the fact
that the
opposite directions. So
collisions between electrons and ions allow cross-field
diffusion to occur. However, the cross-field mobility is
zero, in the lowest approximation, because the vE drifts
+
are equal. Consider what would happen if an ambipolar
field were to build up in the radial direction in a cylindri+
cal plasma. An E-field across B cannot move guiding
centers along E, but only in the E B direction (Sec. II4). If ions and electrons were to diffuse at different rates
toward the wall, the resulting space charge would build
up a radial electric field of such a sign as to retard the
faster-diffusing species. But this E-field cannot slow up
those particles; it can only spin them in the azimuthal
direction. Then the plasma would spin faster and faster
Collisions between positive and
negative particles cause both guiding until it blows up. Fortunately, this does not happen becenters to move in the same direction, cause the ion and electron diffusion rates are the same
resulting in cross-field diffusion.
across B in a fully ionized plasma. This is not a coincidence; it results from momentum conservation, there
being no third species (neutrals) to take up the momentum. In summary, for a fully ionized plasma there is no
cross-field mobility, and the cross-field diffusion coefficient, the same for ions and electrons, is given by:
Dc =
n( KTi + KTe )
.
B2
(25)
20
Part A2
as large at that given in Eq. (5).
n
e
Light emission excited by fast electrons shows the shape of the field
lines in a magnetic bucket.
21
100.00
Argon Momentum Transfer Cross Section
Square angstroms
10.00
1.00
0.10
0.01
0.00
0.01
0.10
1.00
Electron energy (eV)
10.00
100.00
16
Elastic collision cross section
electrons on neutral argon
(numerical fit)
(10
-16
cm2)
12
0
0
20
40
60
80
100
22
Part A2
8
n0<v> (MHz)
6
Ar
H2
He
Ne
0
0
Te (eV)
10
1.0
ion (10
-16
cm )
10.0
0.1
0.0
10
100
Electron energy (eV)
1000
23
Ionization probability in argon
1E-04
1E-08
1E-12
<>
1E-16
1E-20
1E-24
1E-28
1E-32
0
KTe (eV)
10
100
Xe
4
Kr
Ar
Ne
(10
-16
-2
cm )
He
2
1
0
0
20
40
60
80
100
Electron energy (eV)
120
140
160
24
Part A2
14
Excitation cross section for Argon 488 nm line
12
(10
-18
cm2)
10
6
4
2
0
15
20
25
E (eV)
30
35
Plasma Sources I
25
HELICO
ICP
Maximum useful
density at wafer
level
ECR
RIE
1E+08
1E+09
1E+10
1E+11
1E+12
1E+13
n (1010cm-3 )
4
3
2
900 W
600 W
300 W
-12
-8
-4
r (cm) 0
12
26
Part A3
PLASM A
+
+
+
SHEATH
+
Cl atom
+ IO N
Photoresist
Silicon
or SiO 2
Substrate
bird's beak
Gate oxide
conduction channel
to source
Polysilicon substrate
Field oxide
to drain
Plasma Sources I
27
rameters, such as magnetic field shape and independent
power sources, to make them more versatile.
Reliability. In a factory, equipment failures cause
expensive delays. Simple design can lead to more reliable plasma sources.
Small footprint. Compactness is an important attribute when hundreds of machines need to be housed in
a fabrication facility.
Benign materials. To keep contamination down,
very few materials are admissible in a plasma source.
Since the wafer is silicon, Si walls are desirable. Often,
glass or quartz, which are mostly Si, are used. Aluminum and alumina are common wall materials. Plasma
sources which require internal electrodes would introduce metals into the chamber.
2. Elements of a plasma source
There are four main subsystems to a plasma
source: the vacuum system, the gas handling system, the
cooling system, and the discharge power source. Plasmas that require a magnetic field would also need field
coils and their power supply.
Vacuum system
To make a plasma, we must first create a vacuum.
Atmospheric pressure is 760 Torr, and operating pressure
in a plasma reactor is generally between 1 mTorr and 100
Torr. The base pressure, before the chamber is filled
with gas, has to be much lower than the operating pressure in order to keep down the partial pressure of contaminants. Thus, base pressures are at least 10-5, and
sometimes 10-6 (the Torr is understood). This is not usually a problem. Ultra-high-vacuum (UHV) systems can
get down to 10-10, but these are not generally needed.
(High-energy accelerators can get down to below 10-20
Torr, approaching the vacuum of outer space.) The turbomolecular pump, or turbopump, is universally used
nowadays. This has a multi-slotted fan blade that spins
at a high velocity, physically blowing the gas out of the
vacuum chamber. The rotor has to be supported by a
very good bearing, sometimes oil cooled, or by magnetic
suspension. The speed is controlled by an electronic circuit. Old pumps used oil or mercury vapor, which can
get back into the chamber and contaminate it; but turbopumps are basically clean. The fan blade, however,
cannot maintain the large pressure differential between
high vacuum and atmospheric pressure; the air on one
28
PLASMA
SUBSTR ATE
SHU TO FF VALVE
G AUG E
RO UG HIN G
VALVE
TURBO
PUMP
PIRANI GAUGE
IO N
RO UG HIN G
PUMP
Part A3
side would give so much drag that the blade could not
spin at the required speed. So a turbopump has to be
backed up by a forepump, or backing pump. There are
many types of these, but they are all mechanical. For
instance, a diaphragm pump moves a diaphragm back
and forth and valves open and close to move the air from
one side to the other. To pump the corrosive gases used
in plasma processing, all the materials have to be chemically inert, and these dry pumps are considerably more
expensive. The forepump generally provides a pressure,
called the forepressure, of 1 to 50 mTorr, and the turbopump can then maintain the differential between this
pressure and the base pressure.
FO RE PU MP
Plasma Sources I
PO W ER MON ITO RS
29
low. This is desirable, for instance, to keep the wafer
sheath collisionless so that the accelerated ions are not
deflected, or to keep dust particles from forming. Therefore, large turbopumps, with apertures of, say, 12 inches,
and pumping speeds in the thousands of liters per second,
can be found on plasma reactors. The gas handling system, with numerous inputs from tanks of gases, flow
meters and flow controls, and computer interface, can be
a large part of the plasma system.
MATCH BO X
A N TEN N A
REFL.
IN
PLASMA
POW ER
AMPLIFIER
CO AX
CABLE
OSCILLAT OR
Cooling system.
One of the disadvantages of plasma processing is
that a lot of heat is generated. Walls of the chamber are
usually water-cooled. Antenna wires are made of copper
tubes with water flowing through them. The most critical cooling requirement is imposed by the wafer, which
has to be maintained at a given temperature for each
process, and which tends to be heated severely by plasma
bombardment. Helium is introduced to the back side of
the wafer through holes in the chuck which holds it. This
gas is made to flow under the wafer to keep it at a uniform temperature. It is not necessary to create a space
for the helium to flow; the underside of the wafer is usually rough enough.
Discharge power system.
To ionize and heat a plasma, electrical power is
applied either at a radiofrequency (RF) or at a microwave
frequency. The vast majority of sources use the industrially assigned frequency of 13.56 MHz. Some work at a
harmonic or subharmonic of this, and some experimental
sources run at frequencies higher or lower than this
range. Electron cyclotron resonance (ECR) sources are
driven at 2.45 GHz, the same as is used in microwave
ovens.
RF sources are usually driven by a solid-state
power amplifier with a built-in oscillator to generate the
signal. The output into a 50- cable is usually 2 kW or
less. The cable then goes into a matching network, or
matchbox, which performs the important function of
transforming the impedance of the antenna-plasma system to the 50- impedance of the rest of the circuit. Before passing through the matching network, the power
goes through directional couplers which measure the
power flowing into the antenna and back from it. This
reflection has to be kept low (< 1%) to protect the amplifier and to make best use of its power. The main elements of the matching network are two (physically)
30
Part A3
large, adjustable vacuum capacitors. The tuning is done
by varying the capacitances of these two elements. Since
the RF current in the capacitors is displacement current
in vacuum, there is very little power loss in such a circuit. Sometimes a variable inductor is used, consisting of
two coils, one of which can be rotated to change the
mutual coupling. Industrial tools invariably have automatch circuits, in which the tuning capacitors are automatically adjusted by motors driven by a circuit that detects the reflected power and tries to minimize it. Once
the operating conditions of the plasma source are set, the
automatch circuit has no problem finding the minimum
and keeping the system tuned as the plasma conditions
change. However, finding the vicinity of the correct
match may be difficult initially. After the match circuit,
the power is fed to the antenna through cables (several
may be needed to carry the current) or a parallel transmission line. At this point there may be very high voltages, exceeding 1 kV. The length of the line affects the
tuning conditions sensitively. In a capacitive discharge,
the RF is connected directly to the internal electrodes. In
an inductive discharge, the power goes to an external
antenna, which is wound around the chamber in various
ways depending on the type of source. In experimental
systems there may be sensors to measure the RF voltage
and current applied to the antenna.
ECR sources are driven by a magnetron providing
2.45-GHz power, which is transmitted in a waveguide.
A Magic T device serves the function of the matching
network in RF systems. The waveguide then goes to a
horn antenna, which launches the microwave power into
the plasma through a window. This vacuum window is a
critical element, since it has to be made of a material
such as quartz or ruby and tends to crack under high
power. It also can be coated by deposits from the
plasma. Since an ECR source has to strike a cyclotron
resonance, magnetic coils have to provide the resonant
field of 875 G somewhere in the plasma. Magnet coils
are usually water-cooled copper tubes wound with many
turns and held together by epoxy. They are driven by a
low-voltage, high-current power supply such as those
used for arc welding, only with better filtering.
Plasma Sources II
31
SHEATH
1. Debye sheath.
Consider first the sheath on a grounded wafer
bounding a plasma that is not oscillating. Let the plasma
potential (space potential) be Vs and the wafer potential
be Vw < Vs. From our discussion of presheaths in Eq.
(A1-22), the plasma density ns at the sheath edge will be
about n. The ion flux through the sheath from the
plasma to the wafer is given by
i = ns cs , cs = ( KTe / M ) 1/2
(1)
32
Part A4
1/ 2
v 1 2 KTe
vr = =
4 2 m
(2)
Debye
sheath
(3)
KTe m
ln
2e 2 M
Vw Vs =
ChildLangm uir
sheath
(4)
5
= 52 m .
0.1
The sheath thickness s can be obtained only by integration, but it is of order 5D; thus, in this case the Debye
sheath is about 0.25 mm in thickness, and the sheath drop
is about 5 5 = 25 V.
2. Child-Langmuir sheath.
When a voltage is applied between the plates, the
sheath drop cannot be 25 V on both plates; at least one of
them must have a much larger sheath drop to take up the
RF potential of hundred of volts that is applied. These
large potential drops, much larger than KTe, occur in a
layer called a Child-Langmuir sheath, that joins
smoothly onto the Debye sheath and extends all the way
to the wall. This differs from the Debye sheath because
only one charged species, in this case ions, exists in the
C-L sheath, the electrons having almost all been turned
back before they reach it. Those that remain are so few
that they contribute a negligible amount to the charge in
the C-L sheath. The current density j, voltage drop V0,
and thickness d are related by the Child-Langmuir Law
of Space-Charge-Limited Diodes (Chen, p. 294, L & L,
p. 165):
1/ 2
4 2e
j=
9 M
3
0V0 / 2
d2
(5)
Plasma Sources II
33
We can equate this to the ion current density j = enscs and
solve for d; the result is:
1/ 2
4 0 2
d =
9 e TeV
2
3
V0 / 2
.
ns
(6)
2 2V
d= 0
3 TeV
D .
(7)
This formula differs by 2 from standard treatments because we have evaluated D in the plasma proper, not at
the sheath edge, where the density is half as large. As an
example, let V0 = 400 V and KTe = 5 eV; this gives d =
15D, or about 0.8 mm for the example used above.
Thus, the total sheath thickness s + d is about 20D = 1
mm. This is much larger than feature sizes on the chip
but much smaller than discharge dimensions. A density
of 1011 cm-3 is high for an RIE plasma, however; total
sheath thicknesses over 1 cm, an appreciable fraction of
the discharge height, are often seen in RIE discharges at
lower densities and higher temperatures. Note that d
varies as V03/4. This approximation is not really a good
one, as the exact solution (Fig. 3) for the combined
sheaths shows. The slope of 3/4 is followed only in very
Fig. 3. An exact calculation for a thick sheaths at very high potentials.
plane sheath shows that C-L scaling
At the high pressures necessary to get high
is not followed unless the sheath is
plasma densities, the collision mean free path of the ions
very thick (log-log scale).
can be shorter than the sheath thickness. Ions can then
scatter in the sheath, thus making anisotropic etching
more problematical.
1000
C-L
Exact
-eV / KTe
100
10
0.1
x / D
10
100
3. Applying a DC bias
Consider a parallel-plate system with plate A (the
wafer side) grounded. If plate B (the hot side) is also at
zero potential, there will be identical sheaths of ~5KTe
on each. For instance, if KTe = 2 V, Vs VB might be
10V. If plate B is now made more positive, so that VB =
5V, say, Vs VB must still be 10V, so Vs must rise to
15V. This is because if Vs VB were only 5V, more
electrons would flow to plate B than ions, and the loss of
negative charge would immediately raise Vs. On the other
hand, if plate B were to go negative, to 5V, say, Vs need
not change. Vs VB is now 15V, and the extra 5 volts
is taken up by a Child-Langmuir sheath, while Vs is
34
VB = 0
~10 V
V
0
0
KT e = 2 eV
A
VB = 5 V
V
0
0
KT e = 2 eV
A
V B = -5 V
V
0
Part A4
maintained at just below 10V by the sheath on plate A.
Thus, the plasma potential always follows the potential
of the most positive electrode or section of the wall.
With an RF power supply driving plate B with a sinusoidal voltage, Vs will follow the positive excursions but
will remain at the potential set by plate A during the
negative excursions of plate B. Meanwhile, plate A (the
wafer) will have a constant sheath drop (10V in our example) when plate B is negative, but will have a larger
sheath drop with a C-L sheath whenever plate B is positive. Thus, the time-averaged sheath drop will be larger
in the presence of an RF drive, and the average ion will
impinge on the wafer with higher energy. Since the RF
power controls the plasma density also, the ion current
and energy for anisotropic etching cannot be controlled
independently in a single-frequency RIE discharge.
To make this more quantitative and extend the
treatment to asymmetric discharges, let the area of A be
AA and that of B be AB. Thus, when these are equal, we
have two similar plates at the top and bottom of the discharge, and when AB << AA, we have a small plate while
the rest of the enclosure may be grounded. For the present, we do not consider a grounded sidewall, which
would form a third electrode.
Using Eqs. (1) and (3), we can equate the ion and
electron fluxes to both electrodes:
KT e = 2 eV
i = ncs ,
er = nv
(8)
+
-
+
-
PLASM A
SHEATH
2
SHEATH
1
ncs m
eV
A
=
, B < 1.
,
nv 2 M
KTe
AA
(10)
Dividing by AA , we obtain
(1 + ) = e s + e(B s ) .
Plasma Sources II
35
(1 + ) = e
B
A
(1 + e
1 + eB
), s = ln
(1 + )
(11)
(12)
>
,
<.
(13)
1+
= 1
B
A
This means that B cannot draw saturation electron current unless the area ratio is less than , which is 0.0046
for argon. If AB is that small (very unlikely), B is effectively a wall probe, and we shall use probe theory to describe it. For the normal case, Eq. (11) is valid, and Vs
will follow positive excursions in VB.
When no bias is applied (VB = 0), Eq. (11) reduces to
< 1
s = s 0 =
eVs
1
= ln = 5.38 for argon,
KTe
(14)
<< 1
s = s 0 + ln[(1+eB )] .
(15)
36
!
1 + exp(B sin t )
s = ln
.
(1 + )
120
Vs
VB
<Vs-VB>
Vso
-120
0
90
180
270
360
120
1.0
Voltage on B
Fractional current to B
0.0
-0.5
-120
0
90
eB / tot
VB
0.5
180
-1.0
360
270
Part A4
(17)
1.0
Area ratio
eB / tot
1.0
0.1
0.01
0.5
0.0
0
90
180
270
360
AB/AA
Vs
1.0
0.1
0.01
60
0
0
90
180
270
eB
AB er B s
=
e e
tot AA + AB i
1 (1 + )
=
1 + 1 + eB
(19)
360
1
B
e = 1 + 1eB sin t
(20)
Plasma Sources II
37
A real RIE reactor, of course, has walls in
addition to the top and bottom electrodes. If the
sidewalls are insulators, no net current can flow to them,
and therefore their surfaces must charge up to an
oscillating voltage that follows Vs, keeping the sheath
drop at Vs0. This oscillation may couple capacitively
through the sidewalls to ground, in which case the walls
are not completely insulatingthey may be ACgrounded. If the sidewalls are grounded conductors, they
must be treated as a third electrode. Now when different
RF voltages and frequencies are applied to A and B, the
total electron and ion fluxes must be set equal to each
other when summed over all three conductors. The space
potential will oscillate with both frequencies and the beat
between them. The calculation is a trivial extension of
what we have done here so far.
Area ratio
1.0
0.01
0.0001
100
0
0
100
200
300
Peak voltage on B
400
500
Vs
5. Displacement current
VA
VsB
RB
Cp
PLASMA
VsA
CB
RA
Rp
RF
Lp
CA
d = sDebye + dC L ,
(21)
38
Part A4
I d = V / Z = j CV = jV 0 A / d .
(22)
Ii
d
n ecs ncm
Here we have taken f = 13.56 MHz, V 400 V, d 1
mm, and KTe 5 eV in argon. This ratio is unity when n
= 1012 cm-3. In RIE tools, n is much smaller than this, so
that the displacement current is dominant. The power
from the RF source is coupled to the plasma through the
sheath capacitances and drives the plasma current,
carried by electrons, through the plasma, resistively
heating and ionizing it. The sheath conduction currents
discussed in the previous section play only a small rle in
the power balance, though they are responsible for the
rectification effect that produces anisotropic ions.
A more rigorous treatment of the electrical
characteristics of the RIE discharge would require a
circuit analysis of the equivalent circuit including both
the conduction and displacement currents through the
sheath. The fact that the conduction currents are not
sinusoidal would produce harmonics of the RF
frequency. If a bias oscillator is of different frequency is
imposed on the wafer, there will also be beat frequencies.
To prevent the two oscillators from loading each other, a
bandstop filter can be put on each RF supply to prevent
the frequency of the other supply from reaching it. The
Plasma Sources II
39
displacement current can heat the wafer, increasing the
cooling requirements, even though it does not help in
giving the wafer a dc bias. If the bias power is large, it
can heat the plasma and change its density and
temperature.
6. Ion dynamics in the sheath
With the sheath drop Vs - Vw swinging positive
every other half cycle, electron flux to the wafer will
come in pulses. One might think that the ion flux will
also come in pulses. This is not always true: it depends
on the frequency. We consider two extremes. At high
frequency, the ions move so slowly in response to the RF
that they drift more or less smoothly in the average
sheath field rather than the instantaneous one. To see
this, we can calculate the ion motion. Let the sheath drop
be represented by a sinusoidal voltage of 400V peak-topeak, concentrated in a layer about 1 mm thick. The
equation of motion of an ion is then
M (dv / dt ) = eE = eE0 cos t .
(26)
Here E0 has the value (200/103) = 2 105 V/m. Integrating twice over a half cycle, we obtain
dx eE0
=
sin t ,
dt M
eE0
cos t ]0
x=
2[
M
v=
1.3 10
(27)
cm
120
The ions do not all strike the wafer with the same
energy, however, since they have been accelerated different amounts depending on the phase of the RF at
which they enter and leave the sheath. Moreover, the ion
energy distribution is bi-modal, meaning that it has two
peaks with a valley in between. To see how this comes
about, consider the second extreme in which the freFig. 14. Ions hitting the wafer have quency is so low that sheath drop does not change while
an energy depending on the sheath the ions traverse it. Let the discharge be symmetric, so
drop at the time. The number of ions that = 1. Eq. (17) then can be written
Vpeak = 100 V
Ei (V)
< Ei >
Vs0
90
180
270
360
t (degrees)
es =
1
(1 + e sint ) ,
2
(28)
40
Part A4
electrode, the sheath drops being the same but opposite
in phase on each electrode. Since we are neglecting the
transit time, the ion energy Ei at any time is just the
sheath drop eVs = sKTe at that time. Assuming that the
ions enter the sheath at a constant rate, the number of
ions with energy Ei would be proportional to the time Vs
remains at the corresponding value. Thus, on the graph
of Vs vs. t (Fig. 7), which we reproduce in Fig. 14 on an
expanded scale, the number of ions with energy between
Ei and Ei + Ei is proportional to t/Vs, or inversely
proportional to the slope of the curve Vs(t).
To simplify the writing, we introduce the abbreviations
E Ei / KTe = s ,
t ,
a .
(29)
d ( t )
A
=
,
dE
dE / d
(30)
eE =
(31)
(32)
Hence,
f (E) = A
1 + e a sin
,
a cos
= (E) .
(33)
a sin = ln(2 e E 1) .
(34)
Plasma Sources II
41
cos 2 = 1 sin 2 = 1 a 2 [ln(2 e E 1)]2 .
(36)
Hence, finally,
1
2 e E 1
f (E) = A
a 2 [ln(2 e E 1)]2
1+
=A
2 e
1/ 2
(37)
(2 e E 1) a 2 [ln(2 e E 1)]2
1/ 2
There is also a maximum value of E given by the vanishing of the term in curly brackets:
0.05
0.04
ln(2 e E 1) = a ,
2 e E = e a + 1
f (Ei)
0.03
ea + 1
Emax = ln
.
2
0.02
0.01
Emin
0.00
0
(38)
Emax
20
40
60
80
100
120
140
Ei = eVs (eV)
(a)
It would be difficult to integrate Eq. (37) to find the normalization constant A, but there is an easier way. From
Eq. (30), we have
1 = f ( E )dE = A
d
dE = A d = A .
dE
(b)
Fig. 15. Bimodal ion energy
distribution (a) calculated from a
simple model, and (b) measured
experimentally.
[Mizutani et. al.,
JVSTA 19, 1298 (2001)]
where E = Ei / KTe, is the peak RF drive voltage normalized to KTe, and is essentially the square root of the
mass ratio.
The behavior of f(E) can be seen as follows.
This function diverges at Emin and Emax. For small E near
Emin, (2eE 1) is small, and f(E) varies as 1/(2eE 1).
For E near Emax, we may neglect the 1s and ln(2).
Then
f (E)
(39)
2 E2
1 ( Ei2 / V 2 )
The actual f(E) will be smoother than the simplified one shown here, since the ions enter the sheath with
a finite temperature and will also oscillate during their
transit through a thick sheath. One would expect that the
42
Part A4
ions would have the energy of the DC sheath drop,
spread out by the sheath oscillation during their last jiggle. Thus, f(E) will be relatively narrower but still bimodal. The ion flux that provides directionality to the
etching process is therefore not completely controllable;
the ions cannot all have the same energy. In laboratory
experiments it has been shown that changing the bias oscillators waveform to a sawtooth-like wave can produce
a more uniform f(E), but this has not been shown to be
beneficial in practice.
To get an idea of when the analytic solution of
Eq. (40) is valid, consider the ion excursion calculated in
Eq. (27). If we set x equal to the sheath thickness d and
solve for , we obtain 3 108 sec-1, or f 50 MHz.
Thus, unless f << 50 MHz, the spread in Ei will be
smaller than what we have computed neglecting the ion
transit time. This has been confirmed by both computation and experiment.
7. Other effects in RIE reactors
Plasma Sources II
43
incidence. If the sheath field changes in the meantime,
however, the gain and loss may not cancel out. Some
electrons, namely those that enter the sheath when the
field is low and leave the sheath when the field is high,
will have a net gain in energy. Others will have a net
loss, but those that gain energy are important because
they contribute to the tail of the Maxwellian. A few
electrons will have such a velocity that, as they travel
back and forth between the electrodes, they will arrive at
each sheath just at the right phase and experience repeated accelerations. Such collisionless sheath heating
has been treated extensively in theory and computation,
but there has been little experimental evidence of its importance. Perhaps this effect contributes to the fact that
RIE reactors tend to have higher electron temperatures
than other tools.
High pressure discharges
44
Part A4
culating the steady-state equilibrium of RIE discharges.
This fact is dramatically illustrated by the observation of
dust particles.
The nucleation of solid particles in a processing
plasma from molecules produced in etching or deposition
processes occurs by a mechanism that is not yet completely understood. These particles start with submicron, perhaps nanometer, sizes and grow to diameters
of 1 micron or even greater. When they reach macroscopic sizes, dust particles can be seen by sweeping a
laser beam across them. A sheath builds up on each particle larger than D to equalize the ion and electron fluxes
to it, and the particle thus becomes negatively charged,
containing the order of 104 electron charges. This charge
Q can easily be computed, since the capacitance of the
particle is given by CV = Q, where V is the same sheath
drop that we calculated previously for electrodes and
walls. Since the particles are negative, they will accumulate at local maxima of the potential, if there are any.
Otherwise, they can find a stable position above the wafer where the repulsion of the sheath field is balanced by
the downward pressure exerted by the gas flow. By
making grooves in the substrate or inserting dielectric or
other materials under it, it is possible to create a path of
maximum potential which will lead the dust out of the
discharge, but these methods are probably not practical in
large-scale production. When the discharge is turned off,
the negative dust is drawn onto the wafer by the collapsing sheath field, thus destroying any circuits that they
land on. Note that putting the wafer on the upper electrode will not help, since gravity is much weaker than the
electric fields involved. Particulate generation in RIE
discharges is a serious problem that lowers the yield of
viable chips on a wafer. This problem is not as serious in
low-pressure discharges, where dust formation is much
less likely.
The GEC reference cell
RIE discharges were developed by trial and error
without a good understanding of their operation. When
RIE tools were dominant in the industry before the
1990s, many experiments were made to elucidate the
mechanisms in these sources such as those we have discussed here. However, each machine was different, and
it was difficult to draw any universal conclusions. The
participants in the Gaseous Electronics Conference
(GEC) at which many of these results were presented decided to design a standard configuration that everyone
Plasma Sources II
45
could duplicate for their experiments. Thus, the dimensions, materials, and mechanical and electrical design of
this small machine (for processing 4" wafers) were specified. This GEC reference cell served to make observations of one group relevant to those of other groups.
When inductive plasma sources were introduced, however, they differed from one another qualitatively, and,
moreover, their designs were closely guarded secrets.
There is no standard configuration for the more advanced
plasma tools, and their development is pursued independently by each company.
8. Disadvantages of RIE reactors
Since the RF power controls both the plasma density and the oscillations in Vs, the ion flux to the wafer
cannot be varied independently of the ion energy. Capacitive discharges tend to have larger RF electric fields,
and hence the minimum ion energy is relatively high, as
is the spread in ion energies. Being less efficient in ionization than inductive discharges, RIE discharges produce
lower plasma densities and require higher operating pressures. It is then more difficult to avoid ion collisions in
the sheath and the formation of particulates. The electron temperature tends to be higher than in inductive discharges, and this could lead to a larger heat load on the
wafer as well as other deleterious effects such as oxide
damage. There is no obvious way to control the EEDF
so as to adjust the populations of the chemical radicals at
the wafer level. In spite of these disadvantages, RIE reactors are still best for certain processes such as PECVD
(plasma enhanced chemical vapor deposition) where feed
gas can be distributed evenly over a large area by covering one electrode with holes. Contrary to common perception, some RIE discharges are found to cause less
oxide damage than inductive devices. These dinosaurs
are still alive and still incompletely understood. And
they have the advantage of being small and simple.
9. Modified RIE devices
In addition to applying different RF powers and
frequencies to the two electrodes and introducing a
ground electrode, more substantive changes have been
made to RIE reactors to improve their performance. The
most popular of these is the MERIE: Magnetically Enhanced RIE. A magnetic field B is applied to the discharge parallel to the wafer surface. This reduces the
diffusion losses of plasma in the directions perpendicular
to B and enhances the density. The flux of electrons into
46
Part A4
the sheath is also reduced, requiring a smaller Coulomb
barrier, and thus reducing the fluctuation amplitude of
the sheath voltage. However, it has been found that such
a B-field increases damage to thin oxide layers, an effect
attributed to accumulation of charge via the E B drifts
of the electron guiding centers. The plasma as a whole
can become nonuniform because of these drifts. To
avoid this, the direction of the magnetic field can rotated
slowly in the azimuthal direction by using two sets of
field coils separated by 90 and driven 90 out of phase.
Another modification is to insert, half-way between the electrodes, a grounded plate with many small
holes drilled in it. The discharge then tends to break up
into numerous small discharges, one in each hole. These
discharges are intense and can produce a high density
even after diffusing into a uniform plasma at the wafer
level. The plate also serves to isolate the RF fields produced by the primary RF drive and the bias oscillator.
This device is confusingly called a hollow cathode discharge, presumably because real hollow cathode discharges have a source of electrons on axis and a ring or
cylindrical anode (the positive electrode in a DC discharge) surrounding it.
G as inlet
Electrode
RF in
Chuck
Plasma
W afer
He coolant
RF in
G as outlet
47
48
Part A5
magnetic fields, so that B cannot be 875G everywhere.
In a diverging magnetic field, there are resonance zones,
usually shaped like a shallow dish, in which the field is
at the resonance value. Electrons are heated when they
pass through this zone, and the time spent there determines the amount of heating. Note that the microwave
field does not have to be circularly polarized. A planepolarized wave can be decomposed into the sum of a
right- and a left-hand polarized wave. An electron sees
the left-polarized component as a field at 2c and is not
heated by it; the right-hand component does the heating.
A microwave signal at exactly c will not travel, or
propagate, through the plasma. This is because electromagnetic (e.m.) waves are affected by the charges and
currents in the plasma and therefore behave differently
than in vacuum or in a solid dielectric. The relation between the frequency of a wave and its wavelength is
call its dispersion relation. For an e.m. wave such as
light, microwave, or laser beam, the dispersion relation is
c 2k 2 = 2 2
p
or
(a)
Fig. 6. Dispersion curves for (a) the
O-wave, (b) the L and R waves, and
(c) the X-wave.
2
c2 c2k 2
p
= 2 = 2 =1 2 ,
0 v
(1)
where k 2 / . In Part A1 we have already encountered the dispersion relations for two electrostatic waves:
the plasma oscillation ( = p, which does not depend on
k) and the ion acoustic wave ( = kcs, which is linear in
k). The dispersion curve for Eq. (1) is shown in Fig. 6(a)
[from Chen, p. 128]. We see that if < p (the shaded
region), the wave cannot propagate. Its amplitude falls
exponentially away from the exciter and is confined to a
skin depth. It is evanescent. We will need this concept
later for RF sources. This behavior is specified by Eq.
(1), since k2 becomes negative for < p. Note that for
> p the waves travel faster than light! This is OK,
since the group velocity will be less than c, and thats
what counts.
The dispersion curve becomes more complicated
when there is a dc magnetic field B0. For waves traveling along B0, the dispersion relation is
c 2k 2
2
p
1
=1 2
.
2
1 c
(2)
(b)
(c)
49
circularly polarized (R) waves, and the bottom one for
left (L) polarization. These are shown in (b). Of interest
is the R-wave, which can resonate with the electrons (the
solid line). At c, the curve crosses the axis; the phase
velocity is zero. As the wave comes in from the lowdensity edge of the plasma, it sees an increasing n, and
the point marked by R shifts to the right. For convenience consider the diagram to be fixed and the wave to
come in from the right, which is equivalent. After the
wave passes R, it goes into a forbidden zone where k2 is
negative. The resonance zone is inaccessible from the
outside. The problem is still there if the wave propagates
across B0 into the plasma. This is now called an extraordinary wave, or X-wave, whose diagram is shown in
(c). Here, also, the wave encounters a forbidden zone
before it can reach cyclotron resonance.
Fortunately, there are tricks to avoid the problem
of inaccessibility: shaping the magnetic field, making
magnetic beaches, and so on. ECR reactors can operate in the near-field; that is, within the skin depth, so that
the field can penetrate far enough. Though ECR sources
are not in the majority, they are used for special applications, such as oxide etching. There are many other industrial applications, however. For instance, there are
ECR sources made for diamond deposition which leak
microwaves through slots in waveguides and create multiple resonance zones with permanent magnet arrays, as
shown in Fig. 7. By choosing magnets of different
strengths, the resonance zone can be moved up or down.
These linear ECR sources can be arrayed to cover a large
area; as in Fig. 7 and 8.
There are also microwave sources which use surface excitation instead of cyclotron resonance. For instance, the so-called surfatron sources shown in Fig. 9
has an annular cavity with a plunger than can be moved
to tune the cavity to resonance. The microwaves are then
leaked into the cylindrical plasma column to ionize it.
The plasma is then directed axially onto a substrate.
1. Overview of ICPs
Inductively Coupled Plasmas are so called because the RF electric field is induced in the plasma by an
external antenna. ICPs have two main advantages: 1) no
50
Part A5
internal electrodes are needed as in capacitively coupled
systems, and 2) no dc magnetic field is required as in
ECR reactors. These benefits make ICPs probably the
most common of plasma tools. These devices come in
many different configurations, categorized in Fig. 10.
Symmetric ICP
TCP
DPS
In the simplest form, the antenna consists of one or several turns of water-cooled tubing wrapped around a ceramic cylinder, which forms the sidewall of the plasma
chamber. Fig. 2 shows two commercial reactor of this
type. The spiral coil acts like an electromagnet, creating
an RF magnetic field inside the chamber. This field, in
turn generates an RF electric field by Faradays Law:
"
E = dB / dt B ,
z (cm )
(3)
17
(a)
Fig. 11. A commercial ICP mounted
on top of an experimental chamber
(Plasma-Therm)
B-dot being a term we will use to refer to the RF magnetic field. This field is perpendicular to the antenna current, but the E-field is more or less parallel to the antenna
current and opposite to it. Thus, with a slinky-shaped
antenna, the E-field in the plasma would be in the azimuthal direction.
Rather than apply the RF current at one end of the
antenna and take it out at the other, one can design a
helical resonator, which is a coil with an electrical
length that resonates with the drive frequency. The antenna then is a tank circuit, and applying the RF at one
point will make the current oscillate back and forth from
one end of the antenna to the other at its natural frequency. Such a resonant ICP is shown in Fig. 13.
51
52
Part A5
(a)
Fig. 16. Parts of a DPS reactor (Applied Materials).
(b)
Fig. 15. A DPS ICP reactor (Applied
Materials).
53
discussed quantitatively later.
2. Normal skin depth
Just as a plasma can distribute its charges so as
to shield out an applied voltage, it can also generate currents to shield out an applied magnetic field. In Eq. (1)
we saw that electromagnetic waves cannot propagate
through a plasma if < p. More precisely, let the e.m.
wave vary as cos[i(kx t)] = Re{exp[i(kx t)]}. (We
normally use exponential notation, in which the Re is
understood and is omitted.) If k is imaginary, as it is in
ICPs, in which << p, the wave will vary as
skin wall
antenna
x
J
o
x
x
54
Part A5
c2 k 2
= 1
2
p
( + i c )
(5)
c k
p (mTorr)
100
30
10
5
3
1
d s (cm)
10
i
2 1 + c
p
i
2 1 c .
p
2
p i c
1
1
, s =| Im(k ) | c 1 + O c .
k i
2
c 2
100
Argon, 2 MHz, Te = 3 eV
10
n (10 11 cm-3)
100
1000
20
Te (eV)
6
5
4
3
2
1
ds (cm)
15
10
10
p (mTorr)
100
100
|Bz| (mV)
10
p (mTorr)
5
10
20
Calc
0.1
0.01
-15
-10
-5
R (cm)
10
15
(a)
20
n
KTe
Bz
Vs
16
Vs (Volts)
n, KTe, |Bz|
12
8
0
r (cm)
10
15
(b)
Fig. 20. (a) Decay of the RF field
excited by a loop antenna.
(b)
Profiles of n (1011 cm-3), KTe (eV),
plasma potential Vs (V), and Bz
(arbitrary units) in an ICP discharge in
10 mTorr of argon, with Prf = 300W at
2 MHz.
55
field Bz. In the outer 10 cm of the cylinder, the semilog
plot shows |Bz| decreasing exponentially away from the
wall with a scalelength corresponding to ds. (The exact
solution here is a Bessel function because of the
cylindrical geometry.) However, as the wave reaches the
axis, it goes through a null and a phase reversal, as if it
were a standing wave. This behavior is entirely
unexpected of an evanescent wave, and such
observations gave rise to many theoretical papers on
what is called anomalous skin depth. Fast, ionizing
electrons are created in the skin layer, where the E-field
is strong. These velocities, however, are along the wall
and do not shoot the electrons toward the interior. Most
theorists speculate that thermal motions take these
primary electrons inward and create the small reversed
B-field there. This effect, however, should decrease with
pressure, and Fig. 20a shows that the opposite is true.
The explanation is still in dispute. In Fig. 20b, the
exponential decay of Bz is seen on a linear scale. Also
shown is the plasma density, which peaks near the axis.
Since the RF energy, proportional to Bz2, is concentrated
near the wall, as the Te profile confirms, it is puzzling
why the density should peak at the center and not at the
wall. We have explained this effect recently by tracing
the path of an individual electron as it travels in and out
of the skin layer over many periods of the RF. An
example is shown in Fig. 21. The result depends on
whether or not the Lorentz force FL = ev B is
included. This is a nonlinear term, since both v and B
are small wave quantities. This force is in the radial
direction and causes the electron to hit the wall at steeper
angles. The electrons are assumed to reflect from the
sheath at the wall. The steeper angles of incidence allow
the fast electrons to go radially inwards rather than
RF phase
(degrees)
0
180
360
540
720
900
1080
1260
56
Part A5
skimming the surface in the skin layer. Only when FL is
included do the electrons reach the interior with enough
energy to ionize. This effect, which requires nonMaxwellian electrons as well as nonlinear forces, can
explain why the density peaks at the center even when
the skin layer is thin. Because of such non-classical
effects, ICPs can be made to produce uniform plasmas
even if they do not have antenna elements near the axis.
4. Ionization energy.
(a)
(b)
(c)
(d)
57
plate with radial slots. According to our previous discussion, the induced electric field in the plasma is in the
azimuthal direction, following the antenna current.
Electrons are therefore driven in the azimuthal direction
to produce the ionization. As in other ICPs, the skin
depth is of the order of a few centimeters, so the plasma
is generated in a layer just below the quartz plate. Fig.
24a shows the compression of the RF field by the
plasmas shielding currents. The plasma then diffuses
downwards toward the wafer. In the vicinity of the antenna, its structure is reflected in irregularities of plasma
density, but these are smoothed out as the plasma diffuses. There is a tradeoff between large antenna-wafer
spacing, which gives better uniformity, and small spacing, which gives higher density. Being one of the first
commercially successful ICPs, TCPs have been studied
extensively; results of modeling were shown in Fig. 14.
Densities of order 1012 cm-3 can be obtained (Fig. 24c).
Magnetic buckets have been found to improve the
plasma uniformity. There is dispute about the need for a
Faraday shield: though a shield in principle reduces
asymmetry due to capacitive coupling, it makes it harder
to ignite the discharge. If the antenna is too long or the
frequency too high, standing waves may be set up in the
antenna, causing an uneven distribution of RF power.
The ionization region can be extended further from the
antenna by launching a waveeither an ion acoustic
wave or an m = 0 helicon wave, but such TCPs have not
been commercialized. The spiral coil allows the TCP
design to be expanded to cover large substrates; in fact,
very large TCPs, perhaps using several coils, have been
produced for etching flat-panel displays.
TCPs and ICPs have several advantages over RIE
reactors. There is no large RF potential in the plasma, so
the wafer bias is not constrained to be high. This bias
can be set to an arbitrary value with a separate oscillator,
so the ion energy is well controlled. The ion energies
also are not subject to violent changes during the RF cycle. These devices have higher ionization efficiency, so
high ion fluxes can be obtained at low pressures. It is
easier to cover a large wafer uniformly. In remotesource or detached-source operation, it is desired to have
as little plasma in contact with the wafer as possible; the
plasma is used only to produce the necessary chemical
radicals. This is not possible with RIE devices. Compared with ECR machines, ICPs are much simpler and
cheaper, because they require no magnetic field or microwave power systems.
58
Fig. 24. (a) RF field pattern without
and with plasma; (b) radial profiles of
Br at various distances below the antenna, showing the symmetry; (c)
density vs. RF power at various pressures; (d) plasma uniformity with and
without a magnetic bucket. [from L &
L, p. 400 ff.]
Part A5
6. Matching circuits
The matching circuit is an important part of an
ICP. It consists of two tunable vacuum capacitors, which
tend to be large and expensive, mounted in a box with
input and output connectors. At RF frequencies, wires
are not simply wires, since every length of wire has an
appreciable inductance; hence, the way the connections
and ground plane are arranged inside the matchbox requires RF expertise. In addition, industrial plasma reactors have automatch circuits, which sense the way the
capacitors have to be tuned to match the load and have
little motors that automatically turn the tuning knobs.
Design of matching circuits can be done with commercial network analyzers which plot out the Smith chart
that is familiar to electrical engineers. However, we
have derived analytic formulas which students can use
without the expensive equipment (Chen, UCLA Report
PPG-1401, 1992).
The capacitors, called the loading capacitor CL (C1
in the diagram) and the tuning capacitor CT (C2), can be
arranged in either the standard or an alternate configuration. Let R0 be the characteristic impedance of the power
amplifier and the transmission lines (usually 50), and
let R and X be respectively the resistance and reactance
of the load, both normalized to R0. For instance for an
inductive load with inductance L, X is L/R0. These will
change when the plasma is created. For the standard circuit, the capacitances are
C L = [1 (1 2 R) 2 ] / 2 R
CT = [ X (1 R) / CL ]1
Fig. 25. The standard (left) and alternate (right) matching networks.
(6)
CT = ( X B) / T 2 ,
(7)
T 2 R2 + X 2 ,
B 2 R(T 2 R) .
(7a)
where
59
to a resistive load. This is because a wavelength of a
13.56 MHz wave in the cable is only about 5 m, and the
reflected signal arriving back at the tuning circuit would
be changed in phase significantly by a cable length of a
fraction of a meter. How to handle transmission lines is
covered in PPG-1401. Note in Eq. (6) that a capacitive
load would have negative X, and then CT would become
negative; that is, it would require an inductor rather than
a capacitor. Indeed, RIE discharges cannot be matched
by purely capacitive tuning circuits; an inductor has to be
added inside the matchbox. This inductor can be just a
wire loop a couple of inches in diameter, but the coil
must not be distorted or moved by the user, because that
would change its inductance.
60
Fig. 27. Design curves for electrostatic chucks (from PMT, Inc.)
Part A5
then through the wafers cross section from one region to
the next. The plasma is not necessary for the chuck to
hold. The problem is that it is hard to get rid of the
charging after the process is over to release the wafer;
materials of just the right dielectric constant and conductivity have to be used in bipolar chucks.
An ESC consists of a flat plate (with grooves) covered with a layer of dielectric. On top of that is an air
gap, which is just the roughness of the wafer, and then
the wafer itself. The holding pressure of the chuck depends on the thickness tgap of the air gap, and also on the
ratio / t, where is the dielectric constant of the dielectric layer of thickness t. For given values of these parameters, the holding pressure (in Torr) will increase
with chuck voltage. Dielectric constants vary from 3-4
for polyimide insulators to 9-11 for alumina or sapphire.
Chuck voltages can vary from 100 to 5000V. Since the
plasma potential oscillates at the RF and bias frequencies, the required chuck voltage can also vary with RF
power. Figure 27 shows the variation of clamping force
with gap thickness and voltage with / t.
Plasma Sources IV
.
61
m=1
m=0
Fig. 1. Instantaneous E-field patterns
for m = 1 and m = 0 helicon waves.
1
cos
c 2k 2
(1)
62
Part A6
c 2k 2
2
p
2 c cos
(2)
(3)
ne0
,
k B
2
2 k + k 2 .
(4)
--
Half helical
(5)
Plasma Sources IV
63
while m = 1 is a mode that varies as cos and is RH polarized ( increases as t increases). Similarly, m = 1 is
LH polarized. Though LH waves in free space are evanescent, both RH and LH waves can propagate in a cylinder. Actually LH waves are not easily excited, for obscure reasons.
The electric field patterns for m = 1 and m = 0
helicons are shown in Fig. 1. The m = 1 mode has a pattern that does not change as it rotates. As the wave
propagates in the z direction (the direction of B), a stationary observer would see the pattern rotating clockwise
as viewed along B. The m = 0 mode is entirely different:
the pattern is not invariant but changes from electrostatic
(radial E-lines) to electromagnetic (azimuthal E-lines) in
each half-cycle.
Antennas can be shaped to launch particular
modes. Some are shown in Fig. 2. For instance, a simple hoop or two separated hoops with current in opposite
directions can launch m = 0 modes. A Nagoya Type III
(N3) antenna has two parallel legs connecting two such
hoops; these legs are actually more important than the
end rings. The N3 launches plane-polarized |m| = 1
modes consisting of equal amplitudes of m = +1 and m =
1. In practice, however, the m = 1 mode can hardly be
detected, and the m = +1 mode is the one that is launched
in both directions. A half-helical (HH) antenna is an N3
antenna with one end twisted 180 to match the helicity
of the m = 1 wave pattern. Like the N3, it is half a
wavelength long, chosen to give the right value of kz in
Eq. (3). Depending on the direction of B0, the HH
launches an m = +1 wave out one end and a (small) m =
1 wave out the other. The double saddle coil is an N3
antenna with each parallel leg spit into two paths, slightly
separated. The advantage of this is that it can be slipped
onto a tube without breaking vacuum. With helical antennas, one does not really have to build antennas with
different directions of twist. To change between m = +1
and m = 1 excitation, one merely needs to reverse the
magnetic field. This can be seen from Eq. (5), since the z
direction is defined to be that of B0.
3. Mode jumping
64
Part A6
satisfying Eq. (4) (Fig. 3a). From then on, n increases
linearly with B. Similar jumps are seen as Prf is increased (Fig. 3b). At low power, there is only capacitive
coupling, and the density is very low. As the power is
raised to 100-300 W, inductive coupling takes hold, and
the density jumps to a value characteristic of ICPs. At
400 W or so, the helicon mode is struck, and the density
takes another jump to a value satisfying (4). In Fig. 4,
we see that, as B0 is raised from 0, the density on axis
can increase by 20 times over its B0 = 0, or ICP, value.
However, the averaged density is not changed quite as
much. What happens is that the plasma snaps into a big
blue mode with a bright, dense central core. This core
has a higher Te and higher ionization fraction than the
surrounding plasma. For processing purposes, however,
the >1013 cm-3 densities of the blue mode at 1000G and
2kW are not useful. Lower B0 and Prf are used to create
a weaker, pinkish (in argon) plasma which will dissociate
a molecule like Cl2 but not totally ionize it.
kz = 0
B(G)
0.8
0
100
1000
2000
|Bz|
0.6
0.4
0.2
0.0
0.0
0.2
0.4
r/a
0.6
0.8
1.0
1.0
Kz (cm-1)
0.14
0.12
0.10
0.05
0
0.8
|Bz|
0.6
0.4
0.2
0.0
0.0
0.2
0.4
r/a
0.6
0.8
1.0
5. Trivelpiece-Gould modes
With the same amount of power deposited into
the plasma, helicon discharges produce more ions than
do ICP discharges; it is not just the peak density that is
higher. This was hard to understand, since the usual
transfer of rf energy to the plasma is through collisional
damping of the wave fields, and it can be shown that this
damping is quite weak for helicon waves. Magnetic confinement helps a little (not nearly enough); on the other
hand the field prevents the drift of fast electrons into the
Plasma Sources IV
65
center, as in ICPs. At first, it was thought that Landau
damping was responsible for the efficient energy transfer. This is a mechanism in which electrons surf on the
wave and gain energy up to the phase velocity.
100
= c / 2
B (G)
19
10
50
100
-1
k (cm )
kmin
200
kmax=
500
1200
Kmax
T-G branch
Helicon branch
0
0
10
(cm1 )
100
1000
500
400
300
P(r)
2B + 1B = 0, 2B + 2B = 0 ,
200
100
0
0.00
0.01
0.02
r (m)
0.03
0.04
0.05
(a)
3000
(6)
4
1 1 0
k
1/ 2
.
c
(7)
2000
P(r)
0
0.00
0.01
0.02
r (m)
0.03
0.04
0.05
In Fig. 7, for a given value of k, there are two possible s: 1 and 2. The smaller one has longer radial
66
Fig. 10.
Transition between capacitive coupling (E-mode), ordinary
inductive coupling (H-mode), and
helicon coupling (W-mode) [Degeling
et al., Phys. Plasmas 3, 2788 (1996)].
Part A6
wavelength and is the helicon (H) wave; the larger has
shorter radial wavelength and is the TG wave. Its wavelength can be so short that it damps out before going far
into the plasma, and it is then essentially a surface wave.
Nonetheless, because it is damped rapidly, it accounts for
the efficient RF power absorption of the HWS. The
mechanism is as follows. The antenna excites the H
wave as usual, but the H wave is damped so weakly that
it cannot account for all the RF power absorbed. For >
0, however, the H wave alone cannot satisfy the boundary condition at r = a; a TG wave must be generated
there as well, with an amplitude determined by the
boundary condition. The TG wave is heavily damped
and deposits RF energy near the surface. At low Bfields, the curve becomes shallower, and 1 and 2 are
close to each other, so that the H and TG waves are
strongly coupled, and both extend far into the plasma.
For c < 2, the H wave becomes evanescent, and only
the TG wave can propagate. At high B0, note that there
is a minimum value of k; that is, the axial wavelength
cannot be overly long.
6. Examples of helicon measurements
Fig. 12.
A Nagoya III antenna
launches m = +1 waves in both directions, as long as B0 is above the
threshold for the W-mode.
Plasma Sources IV
67
Fig. 15. Measured radial density profiles of Bj, compared with the Bessel
solutions for m = +1 and m = 1 (faint
line). Regardless of the direction of
B0, it was not possible to get profiles
agreeing with m = 1.
1.8
Prf (W)
n (1011 cm-3)
200
135
115
85
70
1.2
45
0.6
0.0
0
20
40
60
80
100
120
140
B (G)
40G
(b)
12
Jz (arb. units)
10
8
n (1011)
4.2
4.2
no TG
4
2
0
-6
-4
-2
0
r (cm)
68
Part A6
make the magnetic field diverge rapidly, so that very little field exists at the wafer. The density profile can be
flattened by controlling the ratio of the currents in the
two coils. The magnetic fields used in these reactors is
in the 100-400G range.
40
30
20
CCR = -3.0
R (cm)
10
0
CCR = -2.0
-10
-20
-30
-40
Magnitude of B at z = 30 cm
-20
|B| (G)
CCR
-2.5
-1.5
-2.0
0
-25
-15
-5
R (cm)
-10
-5
10
z (cm)
15
20
25
30
35
40
Fig. 21. The B-field patterns in the MRI source (on its side)
for various coil current ratios (CCR). A negative ratio bends
the field lines away from the substrate and can be adjusted to
give < 1G at the wafer level.
-15
15
25
Plasma Sources IV
69
12
ARGON
n (1011 cm-3)
10
P(kW)
3
2
1
8
6
4
PERMANENT MAGNETS
Center
0
0
10
15
R (cm)
20
25
30
ROTATING PROBE ARRAY
20
2
5
8
11
14
17
0
-20
20
-20
70
Part A6
dN
= Ans cs = Ag1ncs Ancs .
dt out
(8)
(9)
KTe (eV)
100
10
1
0.01
0.1
1
p0 (mTorr)
10
100
< v >ion
g1 A
= nn
nn f (Te ) ,
g2 V
cs
(10)
Plasma Sources IV
71
current applied to the antenna times the cosine of the
angle between them. The only difference is the power
dissipated by the antennas resistance and the power
radiated away into space (both of these effects are
negligible). This energy in must be balanced with the
energy out.
The plasma loses energy by particle loss and by
radiation of spectral lines. The total energy lost when
each ion-electron pair recombines at the wall can be
divided into three terms:
Wtot = Wi + We + Wc .
(11)
(13)
(14)
2
0 exp(mvx / 2KTe )vxdvx
2
(15)
Since the KTe term of Eq. (14) does not depend on vx, it
factors out, and we have
72
Part A6
w
2
exp( mvx / 2 KTe )vx dv x
0
0 e dw
2
(16)
UdV = UV VdU ,
U =w
dU = dw
dV = e wdw
V = e w
e w wdw = we w
0 e
dw .
Ec (eV)
1000
100
10
1
KTe (eV)
10
(17)
(18)
Plasma Sources IV
73
plasma. If there is no more energy input in the
downstream region, the electron temperature is
determined by a balance between energy loss by
radiation and energy gain by heat conduction. We give
an example of this. The heat conduction equation for the
electron fluid is
d 3
nKTe = Q q = 0 ,
dt 2
(19)
4. Ion temperature
The ion temperature does not play an important
role in the overall equilibrium, and it is difficult to
measure. However, it is interesting because anomalously
high KTi has been observed in helicon discharges, and
this has not yet been definitively explained. Here we
wish to see what KTi should be according to classical
theory. The ions gain energy by colliding with electrons,
which get their energy from the RF field. The ions lose
energy by colliding with neutrals. Since the neutrals
have almost the same mass as the ions, the latter process
will dominate, and Ti is expected to be near T0, the
temperature of the neutrals. The rate of energy gain is
proportional to the difference between Te and Ti:
dTi
ie
= eq (Te Ti ) ,
dt
(21)
74
Part A6
of energy loss is proportional to the difference between Ti
and T0:
dT
i = nn < v >cx (Ti T0 ) ,
(22)
dt
1.2
Ion Temperature in Argon Discharges
1.0
n/n(fill)
0.80
T i (eV)
0.8
0.43
0.33
0.20
0.6
0.09
0.4
0.2
0.0
0
3
Te (eV)
Plasma Diagnostics
75
76
Part A7
Plasma Diagnostics
77
c
.
=
2
k (1 p / 2 )1/ 2
(1)
78
Part A7
Interferometer signal
= (k0 k1)dx ,
Vacuum
Plasma
(2)
1/ 2
n
k1 = k0 1
nc
0
0
x (mm)
(3)
(4)
(5)
We see that the phase shift measures only the line integral of the density, not the local density. If is high
enough that n << nc, Eq. (5) can be Taylor expanded to
obtain
k0
2nc
n( x)dx k0 L
<n>
radians,
nc
(6)
Plasma Diagnostics
79
perfectly parallel. Refraction can cause part of the beam
to miss the collector, and reflections from the chamber
walls can cause spurious waves.
80
Part A7
sembly rather than at the end immersed in the plasma,
which can cause a leak. Only the ceramic part of the
housing should be allowed to enter the plasma. Some
commercial Langmuir probes use a rather thick metal
tube to support the probe tip assembly, and this can
modify the plasma characteristics unless the density is
very low. In dense plasmas the probe cannot withstand
the heat unless the plasma is pulsed or the probe is mechanically moved in and out of the plasma in less than a
second. When collecting ion current, the probe can be
eroded by sputtering, thus changing its collection area.
This can be minimized by using carbon as the tip material. Ordinary pencil lead, 0.3mm in diameter works well
and can be supported by a hypodermic needle inside the
ceramic shield. One implementation of a probe tip assembly is shown in Fig. 9.
v
PROBE
(a)
R
PRO BE
(b)
Fig. 10. Two basic configurations for
the probe circuit.
Plasma Diagnostics
81
R has to be high enough that the IR drop through it does
change the measured voltage. A rough rule of thumb is
that IsatR should be much greater than TeV, or R >>
TeV/Isat, where Isat is the ion saturation current defined
below. The voltage measured is not the plasma potential
but the floating potential, also defined below. The large
value of R means that good frequency response is difficult to achieve because of the RC time constant of stray
capacitances. One can improve the frequency response
with capacitance neutralization techniques, but even
then it is hard to make a floating probe respond to RF
frequencies.
Electron saturation
"Knee"
Transition
Floating potential
Ion saturation
(a)
0.12
0.10
I (A)
0.08
0.06
0.04
0.02
0.00
I e = I es exp[e(V p Vs ) / KTe )] ,
-0.02
-100
-50
(7)
50
(b)
Fig. 11. (a) An idealized I V characteristic showing its various parts;
(b) a real I V curve from an ICP.
KTe
I es = eAne v / 4 = ene A
2 m
(8)
A being the exposed area of the probe tip. Eq. (7) shows
that the slope of the (ln I)Vp curve is exactly 1/TeV and
is a good measure of the electron temperature. As long
as the electrons are Maxwellian and are repelled by the
probe, the EEDF at a potential V < 0 is proportional to
2
2
f (v) e(mv + eV ) / KTe = ee|V |/ KTe e( mv / 2 KTe ) . (9)
82
Part A7
100.0
Ie (mA)
10.0
Maxwellian
Modified data
Raw Data
1.0
0.1
0
10
15
20
Plasma Diagnostics
83
properties. It is better to measure n by collecting ions,
which would give the same information, since plasmas
are quasineutral. More importantly, one should avoid
collecting saturation electron current for more than a few
milliseconds at a time, because the probe can be damaged.
4. Space potential
The time-honored way to obtain the space potential (or plasma potential) is to draw straight lines through
the I V curve in the transition and electron saturation
regions and call the crossing point Vs, Ies. This does not
work well if Ies region is curved. As seen in Fig. 11b, a
good knee is not always obtained even in an ICP with B0
= 0. In that case, there are two methods one can use.
The first is to measure Vf and calculate it from Eq. (A44), regarding the probe as a wall. The second is to take
the point where Ie starts to deviate from exponential
(10)
For detailed references, see F.F. Chen, Electric Probes, in "Plasma Diagnostic Techniques", ed. by R.H.
Huddlestone and S.L. Leonard (Academic Press, New York, 1965), Chap. 4, pp. 113-200.
84
Part A7
0.03
BRL theory
p = 20
Linear fit
Bohm current
Te = 3 eV, n = 4 x 10
12
-3
cm
I (mA)
Vf
Vs
0.00
= 0.74
-0.03
-160
-140
-120
-100
-80 V
-60
-40
-20
20
Vo
a
Rp
(11)
pv0 = ava
2
= mv0 1 +
Va
,
V0
1/ 2
V
v
p = a a = a 1 + a
v0
V0
.(12)
Plasma Diagnostics
85
probe of length L is therefore
= 2 R p L(1 + Va / V0 )1/ 2 r ,
(13)
KTi
r = n
2 M
(14)
= Ap r erf( ) + e [1 erf ( + ) ] ,
a
where
eV p / KTi,
(15)
a2
2
, a = Rp .
2
s a
2 | eV p |
I Ap ne
Ti 0
M
(16)
86
Part A7
tion radius exist, and OML theory is inapplicable.
Nonetheless, the I2 V dependence of Isat is often
observed and is mistakenly taken as evidence of orbital
motion.
ii) ABR theory. To do a proper sheath theory,
one has to solve Poissons equation for the potential V(r)
everywhere from the probe surface to r = . Allen,
Boyd, and Reynolds (ABR) simplified the problem by
assuming ab initio that Ti = 0, so that there are no orbital
motions at all: the ions are all drawn radially into the
probe. Originally, the ABR theory was only for spherical
probes, but it was later extended to cylindrical probes by
Chen1, as follows. Assume that the probe is centered at r
= 0 and that the ions start at rest from r = , where V = 0.
Poissons equation in cylindrical coordinates is
1 V
r
r r r
e
= ( ne ni ) ,
0
ne = n0eeV / KTe .
(17)
= ni vi = I / 2 r , where vi = ( 2eV / M ) .
I 2eV
ni = =
vi 2 r M
Thus,
(18)
-1/2
(19)
e I 2eV
0 2 r M
-1/2
Defining
eV
,
KTe
1/ 2
KT
cs e
M
(21)
KTe 1
e I ( 2 )
r
=
n0e (22)
0 2 r cs
e r r r
or
-1/2
KT 1
I ( 2 )
0 2e
r
=
n0e r r r 2 r n0cs
e .
(23)
Plasma Diagnostics
87
The Debye length appears on the left-hand side as the
natural length for this equation. We therefore normalize
r to D by defining a new variable :
1/ 2
KT
D 0 2e
ne
0
(24)
=
2 r n0cs
I
1
=
( 2 )-1/2 e
2 n0 D cs
1/ 2
I n0e2 M
=
2 n0 0 KTe KTe
( 2 )1/2 e
eI M
e
2 KTe 2 0n0
(25)
Defining
1/2
eI M
J
2 KTe 2 0n0
(26)
= J e .
(27)
88
Part A7
Plasma Diagnostics
89
0, as BRL have done. The BRL predictions have been
borne out in experiments in fully ionized plasmas, but
not in partially ionized ones.
-3
cm )
ABR
Density (10
11
4
3
2
1
0
200
400
600
800
100
P rf (W )
I (mA)
4/3
2.0
1.5
1.0
0.5
0.0
-70
-60
-50
-40
-30
V
-20
-10
10
n (1011cm-3)
5
4
10 mTorr
3
2
1
0
300
450
600
Prf (W)
750
900
iv) Comparison among theories. It is not reasonable to reproduce the ABR or BRL computations
each time one makes a probe measurement. Chen2 has
solved this problem by parametrizing the ABR and BRL
curves so that the Ii V curve can be easily be created for
any value of Rp/D. One can then compute the plasma
density from the probe data using the ABR and BRL
theories and compare with the density measured with microwave interferometry. Such a comparison is shown in
Fig. 20. One sees that the ABR theory predicts too low a
density because orbiting is neglected, and therefore the
predicted current is too high and the measured current is
identified with a lower density. Conversely, BRL theory
predicts too high a density because it assumes more orbiting than actually occurs, so that the measured current
is identified with a high density. This effect occurs in
partially ionized plasmas because the ions suffer chargeexchange collisions far from the probe, outside the
sheath, thus losing their angular momentum. The BRL
theory assumes that the ions retain their angular momentum all the way in from infinity. One might expect
the real density to lie in between, and indeed, it agrees
quite well with the geometric mean of the BRL and ABR
densities.
Treating the charge-exchange collisions rigorously in the presheath would be an immense problem,
but recently Chen et al.3 have found an even easier, fortuitous, way to estimate the plasma density in ICPs and
other processing discharges. The method relies on finding the ion current at floating potential Vf by extrapolating on a graph of Ii4/3 vs. Vp, as shown in Fig. 21. The
power 4/3 is chosen because it usually leads to a straight
line graph. At Vp = Vf, let the sheath thickness d be given
by the Child-Langmuir formula of Eq. (A4-7) with V0 =
Vf. The sheath area is then A = 2(Rp+d)L. If the ions
enter the sheath at velocity cs with density ns = n0cs, the
ion current is Ii = n0eAcs, and n can easily be calculated
from the extrapolated value of Ii(Vf). Note that if Rp <<
d, Eq. (A4-7) predicts the Ii4/3 Vp dependence (but this
is accidental). (Since d D n1/2, n has to be found
by iteration or by solving a quadratic equation.) The
density in a 10 mTorr ICP discharge is shown in Fig. 22,
compared to n measured by microwaves, by probes using
the ABR theory, or by probes using the saturation electron current. The Vf(CL) method fits best, though the fit
90
Part A7
is not always this good. The OML theory (not shown)
also fits poorly. Though this is a fast and easy method to
interpret Isat curves, it is hard to justify because the CL
formula of Eq. (A4-7) applies to planes, not cylinders,
and the Debye sheath thickness has been neglected, as
well as orbiting and collisions. This simple-minded approach apparently works because the neglected effects
cancel one another. From the preceding discussion, it is
clear that the rigorous theories, ABR and BRL, can err
by a factor of 2 or more in the value of n in partially
ionized plasmas. There are heuristic methods, but these
may not work in all conditions. It is difficult for Langmuir probes to give a value of n accurate to better than
1020%; fortunately, such accuracy is not often required.
6. Distribution functions
Since the ion current is insensitive to Ti, Langmuir probes cannot measure ion temperature, and certainly not the ion velocity distribution. However, careful
measurement of the transition region of the I V characteristic can reveal the electron distribution if it is isotropic. If the probe surface is a plane perpendicular to x,
the electron flux entering the sheath depends only on the
x component of velocity, vx. For instance, the Maxwell
distribution for vx is
1
2 2
2
f M (v x ) =
v exp( v x / vth ), vth 2 KTe / m .
th
(28)
The coefficient normalizes f(v) so that its integral over all
vxs is unity. If f(v) is not Maxwellian, it will have another form and another coefficient in front. The electron
current that can get over the Coulomb barrier and be
collected by the probe will therefore be
I e = eAn
v min
v x f (v x )dv x , mv 2 = e(Vs V p ) = eV p
min
(29)
where vmin is the minimum energy of an electron that can
reach the probe, and Vs = 0 by definition. Taking the derivative and simplifying, we find
dI e
dv
d
= eAn
v x f (v x ) x dV p
dV p
dV p vmin
dV p
= eAn v x f (v x )
dv x
dV p
v x =v min
Plasma Diagnostics
91
dI e
e
ne2
= eAn v x f (v x )
=A
f (v min ) ,(30)
dV p
mv x v = v
m
min
x
so that f(vx) can be found from the first derivative of the I
V curve. If the probe is not flat, however, one has to
take the three-dimensional distribution g(v) = 4v2f(v),
where v is the absolute value |v| of the velocity, and take
into account the various angles if incidence. Without
going into the details, we then find, surprisingly, that f(v)
is proportional to the second derivative of the I V
curve:
d 2 Ie
Electron current
2
dV p
-20
-10
Vp - Vs
10
20
30
(a)
Te = 3 eV
Helium
Electron Current
Vrf V)
0
5
10
15
0.3
0.2
0.1
0.0
-0.1
-20
-15
-10
-5
eV/KTe
(31)
0.5
0.4
f (v)
10
(b)
Fig. 25 . (a) The center curve is the
correct I V curve. The dashed ones
are displaced by 5V, representing
changes in Vs. At the vertical lines,
the average Ie between the displaced
curves is shown by the dot. The line
through the dots is the time-averaged
I V curve that would be observed,
differing greatly from the correct
curve. (b) Computed I V curves for
sinusoidal Vs oscillations of various
amplitudes.
7. RF compensation
Langmuir probes used in RF plasma sources are
subject to RF pickup which can greatly distort the I V
characteristic and give erroneous results. ECR sources
which operate in the microwave regime do not have this
trouble because the frequency is so high that it is completely decoupled from the circuitry, and the measured
currents are the same as in a DC discharge. However, in
RF plasmas, the space potential can fluctuate is such a
way that the circuitry responds incorrectly. The problem
is that the I V characteristic is nonlinear. The V is
actually the potential difference Vp Vs , where Vp is a
DC potential applied to the probe, and Vs is a potential
that can fluctuate at the RF frequency and its harmonics.
If one displaces the I V curve horizontally back and
92
Part A7
forth around a center value V0, the average current I
measured will not be I(V0), since I varies exponentially in
the transition region and also changes slope rapidly as it
enters the ion and electron saturation regions. The effect
of this is to make the I V curve wider, leading to a
falsely high value of Te and shifting the floating potential
Vf to a more negative value. This is illustrated in Fig. 25.
Plasma Diagnostics
93
94
Part A7
When the coil is placed in a time-varying magnetic field
B, an electric field is induced along the wire according
to Faradays Law:
E = dB / dt .
(32)
(33)
Here the line integral is along the wire in the coil and
is the magnetic flux through the coil, which is BA,
where A is the area of the coil. The induced voltage Vind
is measured by a high-impedance device like an oscilloscope. If there are N turns in the coil, the voltage will be
N times higher; hence,
!
Vind = NAB
(34)
Plasma Diagnostics
95
The difficult part is to take the signal out through
the probe shaft without engendering too much RF
pickup. One way is to use a very thin rigid coax, which
is then connected to the scope with a 50- cable. The
coil in this case can be a single turn formed from the
center conductor looped around and soldered to the conducting shield. If the shaft has to traverse a long path
through the plasma, a better way is to use a multi-turn
coil to increase the signal voltage, and then bring the two
ends of the coils through the shaft with a twisted pair of
wires. Outside the plasma, the wires are connected to a
balun (balanced-to-unbalanced) 1-to-1 transformer so
that the signal can be carried to the scope with an unbalanced line. Such a probe is shown in Fig. 30. The transformer can also have a turns ratio that amplifies the signal voltage. With magnetic probes there is always the
danger of capacitive pickup through the insulators. One
can check this by rotating the probe 180. The magnetic
signal should be the same in magnitude but shifted 180
in phase, while the capacitive signal would be the same
in both orientations. Whether or not the probe and leads
should be shielded with slotted conductors is a matter of
experimentation; the shield can help or actually make the
pickup worse.
C
G1
G2
G3
2. Energy analyzers
Gridded energy analyzers are used to obtain better data for ion and electron energy distributions than can
be obtained with Langmuir probes. However, these instruments are necessarily largeat least 1 cubic centimeter in volumeand will disturb the plasma downstream from them. A standard gridded analyzer has four
grids: 1) a grounded or floating outer grid to isolate the
analyzer from the plasma, 2) a grid with positive or
negative potential to repel the unwanted species, 3) a
solid collector with variable potential connected to the
current measuring device, and 4) a suppressor grid in
front of the collector to repel secondary electrons. In
Fig. 31, s is the sheath edge. Grid G1, whether floating
or grounded, will be negative with respect to the plasma,
and therefore will repel all electrons except the most energetic ones. One cannot bias this grid positively, since
it will then draw so much electron current that the plasma
will be disturbed. It is sometime omitted in order to allow
slower electrons to enter the analyzer. Grid G1 also
serves to attenuate the flux of plasma into the analyzer so
that the Debye length is not so short there that subsequent grid wires will be shielded out. In the space be-
96
Part A7
hind Grid G1, there will be a distribution of ions which
have been accelerated by the sheath but which still has
the original relative energy distribution (unless it has
been degraded by scattering off the grid wires). These
are neutralized by electrons that have also come through
G1. These electrons also have the original relative energy distribution, but they all have been decelerated by
the sheath. Grid G2 is set positive to repel ions and
negative to repel electrons. For example, to obtain fi(v),
we would set G2 sufficiently negative (V2) to repel all the
electrons. The ions will then be further accelerated toward the collector. This collecting plate C, at Vc, would
collect all the ion current if it were at the same potential
as V2. By biasing it more and more positive relative to
V2, only the most energetic ions would be collected. The
curve of I vs. Vc would then give fi(v) when it is differentiated. When ions strike the collector, secondary electrons can be emitted, and these will be accelerated away
from the collector by the field between C and G2, leading
to a false enhancement of the apparent ion current. To
prevent this, Grid G3 is fixed at a small negative potential (about 2V) relative to C) so that these electrons are
turned back. Variations to this standard configuration are
also possible.
Fig. 32. Energy analyzer with only
one grid and a collector
Faraday shield
o
c ppe i
o
f
r l
In a plasma with RF fluctuations, energy analyzers would suffer from nonlinear averaging, just as Langmuir probes do. Because of their large size, and therefore stray capacitance, it would not be practical to drive
the grids of an energy analyzer to follow changes in
plasma potential at the RF frequency. However, one can
design the circuitry to be fast enough to follow the RF
and then record the oscillations in collected current as a
function of time during each RF cycle. By selecting data
from the same RF phase to perform the analysis, one can,
in principle, obtain the true energy distribution. This
technique cannot be used for Langmuir probes, because
the currents there are so small that the required frequency
response cannot be obtained. RF-sensitive energy analyzers have been made successfully by at least two
groups; one such analyzer is shown in Fig. 32.
3. RF current probe
Return loop
Plasma Diagnostics
97
then measured in an external circuit. The coil must take a
return loop the long way around the torus to cancel the
B-dot pickup that is induced by B-fields that thread the
hole. Current probes are usually large and can be bought
as attachments to an oscilloscope, but these are unsuitable for insertion into a plasma. The probe shown here is
not only small (~1 cm diam) but is also made for RF frequencies. It is covered with a Faraday shield to reduce
electrostatic pickup, and the windings are carefully calibrated so that the B-dot and E-dot signals are small compared with the J-dot signal. An example of a J-dot
measurement was shown in Fig A6-17.
Fig. 34.
Schematic of a POP
[Shirakawa and Sugai, Jpn. J. Appl.
Phys. 32, 5129 (1993)].
99
100
Part B1
UV
Photoresist coating
& development
Mask
Photoresist
plasma
Photoresist ashing
plasma
Range
Pressure
0.001-10 torr
Electron density
Low density
109-1011 cm-3
High density
1011-1013 cm-3
Average electron energy
1-10 eV
Average neutral/ion energy 0.025-0.05 eV
Ionized fraction of gas
Low density
10-7-10-5
High density
10-3-10-1
Neutral diffusivity
20-20,000 cm2/s
Free radical density
5-90%
Power dissipation
0.1-10 W/cm2
Deposition:
- Semiconductor (silicon)
- Metal (aluminum, copper, alloys)
- Dielectric (silicon dioxide, silicon nitride,
metal oxides, low-k dielectrics)
Etching:
- Semiconductor (silicon)
- Metal (aluminum, copper, alloys)
- Dielectric (silicon dioxide, silicon nitride,
metal oxides, low-k dielectrics)
Ashing:
- Photoresist removal
- Photoresist trimming
Implantation:
- Dopant ion implant (B+, P+, As+ etc.)
Surface Cleaning / Modification:
- Contamination removal
- Modification of surface termination
In each the plasma is used as a source of ions and/or
reactive neutrals, and is sustained in a reactor so as
to control the flux of neutrals and ions to a surface.
The typical ranges of properties for a glow discharge
used in microelectronic fabrication are as shown in
Table 1.
In sputtering processes (Fig. 4), ions are
extracted from a plasma, accelerated by an electric
field, and impinge upon a target electrode composed
of the material to be deposited. The bombarding
ions dissipate their energy by sputtering processes in
which the surface atoms are ejected primarily by
momentum transfer in collision cascades. The
ejected atoms are deposited upon wafers that are
placed within line-of-sight of the target electrode,
thus facilitating the vapor transport of material
Ta
Ar
Si
+ e
+
+
e-
+
e-
e-
+
+
e+
sheath
feature
Si
Silicon
101
102
Part B1
e
bulk plasma
e-
+ e
e-
+
+
Cl+
Cl
ee+
e-
Cl2
SiCl2
sheath
mask
SiCl4
+
poly-Si
Cl
Si + 4Cl SiCl4
SiO2
oxide
O2 + e 2O + e
e-
+ e
+
+
e-
e-
ee-
+
+
sheath
Resist + O CO2 + H 2 O
Si
Silicon
103
n(r, t ) =
f e dv
(1)
(a)
(b)
dz
dvx
dy
dx
dx
Fig. 1.
Differential volume for electron
balance: (a) three-dimensional x-y-z phase
space, (b) one-dimensional x-vx phase space.
The solid arrows indicate particles entering
the differential volume, while the dotted
arrows indicate particles leaving the
differential volume.
n < >=
f dv
(2)
< v >= v =
1
vf e dv
n -
(3)
(r, t ) = nv =
vf dv
e
(4)
(5)
The first term represents the unsteady-state fluctuations in the element, i.e., the change in the number
104
Part B2
of electrons within the volume that have a certain
velocity. The second term represents the convective
flux of electrons in space due to the net number of
electrons lost or gained by movement of electrons to
and from the volume. The third term is the convective flux of electrons from the volume caused by
their coupling to the electric field, due to their acceleration by the electric field. If there is only an eleceE
. The right-handtric field, we can write a as
m
side term accounts for the transfer of electrons to
and from the differential volume by collisions. The
collisions can be quantified as:
f e
= dv f e fT f e fT vR c 2 sin d
t c
(6)
105
(8)
i
i
f ei v
eE 2 a f ei
+ r fe a
( v fe ) = t + fte + fte
t 3
3mv 2 v
cc
elastic
inelastic
f e a
f a
f e a
eE f e i f e a
+ v r f ei
=
+ e
+
t
m v t cc t elastic t inelastic
(9)
f ei
eE
m( m i ) v
(10)
106
Part B2
electron energy by elastic collisions, and neglect the
spatial variation, the isotropic term of the distribution function can thus be calculated, and is found to
be of the same form as that under a dc field with an
effective amplitude Ee given by
Ee = Eo
2
m
2
2( m + 2 )
(11)
kT f ei f ei
=
=0
m v t c
(12)
mv 2
2 kT
(13)
where the constant C can be determined by the normalization condition. Under these conditions the
electrons are in equilibrium with the gas molecules
and can be characterized by T, the gas temperature.
We will expand our discussion on MBD later.
Case (b): If the electric field strength is low,
few electrons will suffer inelastic collisions, since
the energy transition for inelastic excitation processes will exceed the energy of most electrons. The
Boltzmann equation for this condition after one integration becomes:
f ei e 2 Ee2 M
+ kT + mvf e i = 0
2 2
v 3m m
(14)
mvdv
f e i = C exp
(15)
o
e 2 Ee2 M
kT + 3m 2 2
m
107
where the constant C can be determined by the normalization condition.
Case (c): When the elastic collision losses become dominant compared to the thermal energy exchange with the gas, the applied field is sufficiently
e 2 Ee2 M
large so that
! kT , and the field oscillation
2
3m 2 m
frequency is much less than that of the collision fre1
quency ( 2 " v 2 , i.e., Ee2 = Eo2 ), the solution of
2
the Margenau distribution can be approximated as:
v
mvdv
f e i = C exp 2 2
o e Eo M
2
6m 2 m
(16)
mv 2
f e i = C exp 2 22
e Eo M
6m 2 2
m
(17)
(18)
Since the collision frequency m is proportional to the density of gas particles with which the
electrons collide, it is proportional to the pressure, p.
The electron energy, KT, is, therefore a function of
the electric field to pressure ratio, Eo/p. It should be
remembered that in this model, the energy losses
due to inelastic collisions are assumed to be less
than those due to elastic collisions. This solution is
only applicable to very low Eo/p where the electron
temperature is low and few inelastic collisions occur.
Case (d): If the collision cross-section is as-
108
Part B2
sumed to be independent of the electron velocity, the
collision frequency is proportional to the velocity
and the Margenau distribution becomes the Druyvesteyn distribution of the following form:
mv 2 2
2
i
f e = C exp 2 2
e Eo M
2
6mN 2 m
(19)
109
n/N, as a constant Eo/p=28.3 V/cm-torr. As the ionization increases, the distribution becomes more
Maxwellian-like. This is a result of the increased
electron-electron scattering making the energy exchange within the electron population rapid and
thereby forming an electron gas like distribution and
reducing the importance of the accelerating fields on
the electrons.
The effect of electron interactions on the average energy of the plasma is shown in Fig. 4. The
electron temperature is quite invariant with the
power (i.e., plasma density) for plasmas of sufficient
densities, but is largely a function of Eo/p.
Fig. 3: Effect of the extent of ionization on the
In conclusion, due to inelastic collisions, the
energy distribution function for a hydrogen energy typically is not proportional to the square of
plasma; E/p = 28.3 V/cm-torr (H. Dreicer).
the Eo/p as suggested by Margenau and Druyvesteyn
equations, but increases with a power varying between 0.5 to 1.
II.
110
Part B2
v1
v2
(20)
do
Fig. 5. Illustration of molecular interactions.
(21)
p
c
(22)
Boltzmann relation:
ne (r ) = no e
eV ( r )
KTe
(23)
Mv 2
M 2 2
P(v) = 4
v exp
2 KT
2 KT
(24)
where K is Boltzmann's constant, T is the temperature of the gas, and M is the mass of the gas particles. A plot of the Maxwell Boltzmann distribution
is shown in Fig. 6. This distribution is sometimes
referred to as the Boltzmann distribution or the system can be said to be Maxwellian. The most probable (mp), mean (m), and root-mean-square (rms)
velocities are shown in Fig. 6:
vmp =
2 KT
M
(25)
111
__
8 KT
M
vm = v = vP(v)dv =
o
vmp
vrms
vrms
Probability
vm
2v m
0
200
400
600
800
1000
1200
= v 2 P (v )dv
o
3KT
M
(26)
(27)
y
x
3. Energy Content
The energy content of the gas in both models
is assumed to be entirely associated with the translational energy of the gas particles (i.e., we neglected
rotational, vibrational, and electronic energy). In
SGM, since the particles are all going at the same
speed, they have equal energies:
Energy =
______
2
mv
4 KT
=
2
(29)
mv
=
2
mv 2 P(v)dv
2
3KT
2
(30)
112
Part B2
4. Collision Rate Between Molecules
The collision rate between molecules determines the rate at which energy can be transferred
within a gas, and the rate at which chemical reactions can take place. To derive the frequency of
collisions between gas molecules in SGM, consider
a molecule going in the +z direction. In the simplified model, it will have no collision with any other
molecules going in the +z direction, since they are
all going at the same speed. It will have a closing
speed of 2 relative to that of the n/6 molecules going
in the -z direction, and a speed of 2v relative to the
4n/6 molecules going in the x and y directions.
Therefore, during a given period of time, the molecule sweeps out a cylindrical volume using do as the
diameter and with a length equal to the relative
speed multiplied by the time. The molecule will suffer a collision if its center comes within a distance do
of another molecule's center (Fig. 8). The number of
collisions per unit time is thus, the swept volume
multiplied by the number of molecules per unit volume:
The number of collision is:
_
_
n
4n
= d o2 2 v + d o2 2 v
6
6
_
8 KT
8
= n d o2 v = n d o2
= pd o2
m
mKT
where
L = v t
Fig. 8. The volume swept by a molecule equals
d o2 ( speed )t .
1 2
= +
2 = 1.276
3 3
p = nKT (ideal gas law)
(31)
(32)
= 4 pd o2
mKT
(33)
For argon at 20C and 1 torr of pressure, the collision frequency is 6.7 106 s-1.
5. Mean Free Path
The mean free path, , is the average distance
traveled by a gas molecule between collisions. It is
a determining factor in the rate at which a gas particle can diffuse within a gas. For a given time increment, a molecule travels a distance equal to its
113
speed multiplied by the elapsed time. During this
time it suffers the number of collisions determined
by the previous derivation of the collision frequency.
Thus, the mean free path, , in SGM is
_
v t v
1
KT
= =
=
=
t n c p d o2
(34)
(35)
dx
(36)
x
P ( x ) = exp
(37)
1
n c
(38)
(39)
114
Part B2
6. Flux of Gas Particles on a Surface
The flux of gas molecules striking a surface
determines the maximum rate at which the gas can
react with the surface, assuming unity sticking probability -- every particle that strikes sticks to the surface. The term flux refers to the number of molecules that impinge on a unit surface area in a unit
time increment (Fig. 10). Since all the molecules
_
n v n 8 KT
Flux =
=
6 6 m
(40)
Using the MBD, the flux is calculated by integrating over the velocity component perpendicular
to the surface, yielding
_
nv
Flux =
4
(41)
7. Gas Pressure
The pressure exerted by a gas on a surface can
be calculated from the change of momentum that the
gas molecules undergo during collisions with the
surface. For a system in thermodynamic equilibrium, the gas leaving the surface must have the same
speed (and velocity) distribution as that strikes the
surface. Pressure is the force per unit area or the
change in the gas momentum per unit area per unit
time, as shown in Fig. 11:
115
Pressure =
Force
(Momentum change/molecule)Flux
=
Area
Area
nv
p = 2m v
6
_
(42)
8
nKT
3
(43)
p = 2mvP(v)dv = nKT
(44)
which is the ideal gas law. Using the ideal gas law,
the number density, n, of argon at 20C and 1 torr is
3.3 1016 molecules/cm3. To be more accurate, the
van der Waals equation of state takes into account
the repulsive forces at work at short distances which
tends to reduce V and the attractive forces at longer
distances that tends to decrease p:
Fig. 11. Pressure due to the impulse times
the rate of collision with the wall.
nRT
n2 a
(a, b are constants)
p=
V nb V 2
n2
p + a 2 (V nb ) = nRT
(45)
116
Part B2
the viscosity . The form of the flux equations is
shown below.
dT
Heat Flux = q z = k T
(temperature gradient)
dz
dn M
(conc. gradient)
Mass Flux = jz = D i i
dz
dv y
Momentum Flux = pz =
(velocity gradient)
dz
These coefficients can be calculated using the MBD,
yielding:
_
nc v
1
1
kT = v
! proportional to T 2 M 2
3
( )
2
p o d o
v
D=
3
! proportional to T
p 1
(d )
po
(d )
2 1
o
nM v
=
3
! proportional to T
2 1
o
0.01< /L <1
10-4
50
1
R
10-3
5
0.1
T
10-2
0.5
.01
T
10-1
1
.05 .005
.001 .0001
V
V
R = Rarefied flow
T = Transition flow
V = Viscous flow
117
ing the flow characteristics. A no-slip boundary
condition exists at any surface, meaning that the
velocity of the gas is zero at the surface. For most
situations in vacuum systems, the flow is laminar,
and has flow properties similar to that of molasses.
This is an artifact of the independence of gas viscosity with respect to pressure. The fluid flow characteristics are dependent upon the Reynolds number
which is vD/, where is the density per unit volume. A Reynolds number of less than 2000 in a circular conduit indicates laminar flow. At higher
pressures and high velocities, the flow can become
turbulent.
In the molecular flow regime, any sort of continuum model for the flow behavior of the gas
breaks down; the majority of the gas collisions occur
with the walls of the conduit, not between gas molecules. In this regime the pressure does not influence
the flow characteristics, as shown in Fig. 12. These
flow regimes as a function of the gas density are
summarized in Fig. 13.
The flow characteristics in the transition regime are not fully understood. This makes the
analysis of plasma processing challenging since
most of the plasma processes used in microelectronics processing are performed in this regime.
The flow of a gas through a conduit is usually
characterized as a conductance, analogous to the
conductance in an electrical circuit. The conductance, C, is the ratio of the flow rate in units of pressure-volume/time (Q) and the pressure difference:
Q
C=
(46)
p1 p2
Note that the conductance has units of volume/time.
As in the electronic circuits, the overall conductivity
of a system can be calculated using
1
1
1
1
+
+
+ .....
(47)
Coverall C1 C2 C3
Use a circular tube with a length much greater than
its diameter as an example, the conductivity for air
in it in the rarefied regime is given by
=
D3
L
(48)
In the continuum regime, the conductivity is dependent upon the pressure and can be estimated as
118
Part B2
Clong tube =
D 4 ( p1 + p2 )
128 L
2
(49)
av R 2
4
(50)
Q
p
(51)
=
Fig. 14. Molecular transmission probability, a,
of a short tube as a function of the tube length
to radius.
V pV pV
=
=
S pS
Q
(52)
119
ing conditions, and the pumping speed of the system. Fig. 17 shows a schematic of the pressure gradient in a plasma reactor, with one gas injection
port, multiple layers of gas distribution rings (showerhead design), and a pumping port.
III. COLLISION DYNAMICS
Q (Gas throughput)
P (pressure)
V (volume)
S (pumping speed)
(53)
The differential cross section, I (v, ) , is the proportionality constant and is derived as:
h dh
(54)
I ( v, ) =
sin d
therefore the total scattering cross-section, s, is:
s = 2 I ( v, ) sin d
0
(55)
(56)
To solve for the complex scattering trajectories, we can convert the scattering angles from the
laboratory frame (Fig. 19) into the center-of-mass
(CM) coordinates (Fig. 20), and relate the scattering
angles 1 and 2 to the scattering angle in the CM
frame and the two particles masses: m1 and m2:
Fig. 17: Schematic of the pressure gradient in
a plasma reactor.
tan 1 =
sin
m
cos + 1
m2
sin
tan 2 =
1 cos
(57)
(58)
120
Part B2
dh
h
m1
1
m2
U (r ) =
v2 = 0
v2
vR
WR h
2
where WR = mR vR is the kinetic energy of the
C
A=
2
vR
r(t)
Fixed
center
i +1
2
i+2
(61)
U ( r )
r
p// = mRvR
h
(59)
h
mR
C
ri
r(t)
Fixed
center
1 A
I (v R , ) =
i WR
i 1
2+ 2
i
(62)
121
sphere, m1, is moving with speed v1 towards m2. As
shown in Fig. 22, is the angle between the incident
sphere and the line between the centers of the
spheres as they collide. After the collision the
U(r)
v or K
Coulombic
1/r
1/vR4
1/vR3
Perm. dipole
1/r2
1/vR2
1/vR
Induced dipole
1/r4
1/vR
const.
Hard sphere
1/ri
const.
vR
v1
v1
m1
m2
v2
v2 = 0
!
Fig. 22. Illustration of a collision process.
2m1m2
( m1 + m2 )
(1 cos )
(63)
(64)
If the masses of the spheres are the same, the fractional energy transferred is
1
1
mi = mt = (1 cos )
2
2
at low scattering angles.
This expression would apply for the scattering
of ideal-like gas molecules. Note that the fractional
energy transfer is unity for head-on collisions in this
case. In electron-neutral scattering, the masses are
very different and the energy transfer approaches
zero in elastic collision:
mi >> mt
2m
104
M
122
Part B2
3. Inelastic Collisions
In the collision process, energy can be transferred from kinetic energy to internal energy if at
least one of the particles is complex enough to permit such internal energy states. Atomic gases can
undergo electronic transitions where at least one of
the outer electrons is promoted into a higher energy
state. Diatomic or more complex molecules have
rotational and vibrational states that can be excited
by inelastic collisions. The energy separation of
these states increases in order of rotational, vibrational, and electronic excitations. The possibility of
internal energy transfer can be incorporated into the
elastic model described above by the inclusion of a
U term in the energy conservation relation, where
U is the gain in internal energy of the molecule that
was struck:
1
1
1
mi vi2 = mi u i2 + mt u t2 + U
2
2
2
(65)
1 mt
(mi + mt )u t2
2 mi
(66)
1 mt mi
2 m t + mi
2
vi cos 2
(67)
mvi2
cos 2
4
123
have a more continuous spectrum, however, since
more combinations of rotational, vibrational, and
electronic states are allowed, a larger number of
closely spaced states would appear as continuous.
There are a large number of possible processes
that can occur upon collision. They include electron
impact ionization, excitation, relaxation, dissociation, electron attachment, and ion-neutral collisions.
Each of the processes can be quantified with a crosssectional area that is proportional to the rate at
which the collisional process takes place. Gas-phase
reactions, which are often consequences of these
inelastic collisions, are discussed in the following
section.
125
126
Part B3
the total orbital angular momentum is 0, and the
subscript 0 denotes that the total angular momentum
is 0 (J=L+S=0).
Another example: the ground state neutral
carbon and oxygen described by LS coupling
scheme are (1s)2(2s)2(2p)2 3P0 and (1s)2(2s)2(2p)4
3
P2. Here we have 2 electrons in the 1s state, 2
electrons in the 2s state, and 2 or 4 electrons in the
2p state. In addition, the net spin state is triplet
(superscript 3), the orbital angular momentum state
is P (angular momentum quantum number is 1) and
the total angular momentum state is 0 or 2 (for less
than half filled orbital, J=L-S=0; for half filled
orbital or more than half-filled orbital, J=L+S= 1 +
1 =2).
In summary, the designation of atomic energy
levels can be done using the spectroscopic
designation of an atomic state:
X I n 2 S +1LJ
Fig. 1. Atomic energy levels for the central field
model of an atom (e.g., Na).
e
Fig. 2. An electron atom elastic collision.
127
e + A ! e + e + A+
*
e
128
Part B3
e + A* ! e + e + A+
Electrons with sufficient energy can also remove
an electron from a metastable atom and produce
one extra electron and an ion. Since the
metastable atom is already excited, less energy
is required here to ionize the atom.
A* + B ! A + e + B+
Metastable atom can collide with a neutral and
ionize it if the ionization energy of the neutral
(B) is less than the excitation energy of the
metastable (A*). This is also called the Penning
Ionization process.
2. Relaxation and Recombination Processes
a) De-excitation (Fig. 8):
A* ! A + h
Fig. 8. De-excitation.
e + A+ ! A + h
Photon can also be generated during the
coalescence process of recombination. This is
also a three-body recombination process, since
the two-body coalescence is highly unlikely
from the standpoint of energy and momentum
conservations.
d) Electron attachment (Fig. 11):
e + A ! A
129
Electron can attach to an electronegative atom to
form a negative ion, for example, a halogen
atom or an oxygen atom.
Complex gas
molecules such as SF6 can also undergo
dissociative attachment to form negative SF5
ions.
This could also be a three-body
recombination process.
e) Ion-ion recombination (Fig. 12):
A+ + A ! A + A
With negative ions generated, positive ions and
negative ions can collide with finite (usually
small) probabilities. In ion-ion recombination,
one electron transfers and two neutrals are
formed.
III. ELASTIC COLLISIONS
1. Coulomb collisions
In general, collisions between ion-ion, ionelectron, and electron-electron are all Coulombic
collision. The coulomb potential is:
U (r ) =
q1q 2
4 0 r
(1)
b2
0
I (v R , ) =
4 sin 2
(2)
q1q2
=
4 0WR
Z1Z 2 e 2
1
2
4 0 mR vR
2
(3)
130
Part B3
a
qo r
d q
(5)
qo 2 a 3
8 0 r 4
(6)
H
C
N
O
Ar
CCl4
CF4
CO
CO2
Cl2
H2O
NH3
O2
SF6
4.5
12
7.5
5.4
11
69
19
13
17
31
9.8
14.8
10.6
30
mR =
m1 m2
m1 + m2
v R = v1 v 2
(8)
(9)
(10)
(11)
131
132
Part B3
450
550
706.5 nm He I 2 P-3 S
1
1
1
1
500
667.8 nm He I 2 P-3 D
400
501.6 nm He I 2 P-3 P
3
3
402.6 nm He I 2 P-5 D
Intensity
350
587.5 nm He I 2 P-3 D
447.1 nm He I 2 P-4 D
600
650
700
Wavelength (nm)
Fig. 15. Emission from a He Plasma.
750
133
ground state electron in the atom to an excited state.
The energy required for this excitation is fairly
large. For example, in hydrogen atom, a minimum
energy of 10.2 eV is required to move the electron
from the ground state (1s) to the lowest excited state
(2p) from which atom can emit the photons. An
ionization process requires more energy than the
excitation process (for example, the ionization
potential of hydrogen is 13.6 eV). The ionization
cross-sections of several noble gases and the
excitation corss-section for H are shown in Fig. 17
and Fig. 18 as examples.
Once the atoms in the plasma are excited
above the ground state, it will eventually be deexcited to the ground state. There are three
different ways to de-excite the atoms in the plasma.
The first one is the spontaneous emission when the
electron in the excited level makes a transition to
the ground level or another excited level without
any external influence. As briefly mentioned
earlier, the time scale for this de-excitation is very
short if the transition is electric dipole transition, on
the order of 10-8 sec to 10-7 sec. In this case, the
energy conservation is satisfied by emitting the
photon whose energy is equal to the energy
difference between the initial state and the final
state. In many plasma systems, this is the most
important de-excitation mechanism. On the other
hand, the electron in the excited level also makes a
transition if there are other photons around the
excited atoms. This process is called stimulated
emission. Though the stimulated emission is the
key element for the laser, in most plasma system,
the stimulated emission can be neglected. The third
process for the de-excitation is the inverse process
of the collisional excitation and is called collisional
de-excitation.
In collisional de-excitation, the
colliding particles will gain energy from the excited
atoms into their kinetic energy. The importance of
collisional de-excitation is a function of plasma
density and electron temperature and it varies for
various excited states.
3. A simplified model for emission
To simplify the discussion, we will make a
number of assumptions on our plasma system.
1. Plasma density (ne) is uniform throughout the
volume.
2. Electron energy distribution is Maxwellian and
134
Part B3
its temperature is given as Te.
3. Our plasmas are made of hypothetical atoms that
have only 4 energy levels, ground state, first and
second excited state and ionized state.
4. The rate of collisional de-excitations are small
compared to the rate of spontaneous emission,
thus will be neglected.
5. The system is in steady state.
As shown in Fig. 18, Eo, E1, E2, and Ei are the
ground state, excited state 1, excited state 2, and the
ionized state. R1, and R2 are rate of collisional
excitation from the ground state, and A1o, A2o, and
A21 are rate of spontaneous emission (Note that they
are also called Einstein A coefficient). R1, and R2
can be calculated using the collisional crosssections:
R1 = ne n0 < 1v >
R2 = ne n0 < 2 v >
Remember <v> is the collision rate averaged over
the MBD.
From these rates, the equations governing the
density of each state can be determined:
Ei
R2
R1
E2
A21
A2o
A1o
E1
Eo
dn0
= ne n0 (< 1v > + < 2 v > ) + n1 A10 + n2 A20
dt
dn1
= ne n0 < 1v > + n2 A21 n1 A10
dt
dn2
= ne n0 < 2 v > n2 ( A21 + A20 )
dt
135
at these frequencies, we can then determine the
density of excited states (n1 and n2) independently:
# photons at 10
= n1 A10 volume
time
# photons at 20
= n2 A20 volume
time
136
Part B3
Fig. 19. He Grotrian Diagram
137
Repulsive state
Bonding state
v=6
v=5
v=4
v=3
v=2
v=1
v=0
R
Zero-point energy
v=0
hv v +
2
h2
138
Part B4
5
0
10
5
0
A
J
10
J
J
J
10
J
5
10
10
5
0
10
5
0
5
0
X
Fig. 4. Vibrational and rotational energy
levels.
139
molecule (Fig. 2). Note that the lower energy level is
typically labeled as v" and higher energy level is labeled
as v ' , as shown later in Fig. 4.
3. Rotational energy level
For a simple dumbbell model for diatomic
molecules, the moment of inertia is I = mR r 2 . The
rotational energy level is:
h2
Bv J ( J + 1)
8 2 I
Therefore, the energy spacing increases with increasing
rational quantum number (Fig. 3). Again, the lower
energy level is typically labeled as J " and higher energy
level is labeled as J ' , as shown in Fig. 4, where the
details of the allowed vibrational and rotational
transitions, spectrum lines, and intensity distribution.
Note that X denotes the ground state, while A represents
an excited state.
Figure 5 shows the theoretical infrared absorption
spectrum of a diatomic molecule, HCl: (a) the allowed
vibrational and rotational transitions, (b) the measured
spectrum lines, and (c) the intensity distribution. Note
that the P branch represents the transitions corresponding
to J=-1, while the R branch represents the transitions
corresponding to J=+1. The Q branch is missing since
the transition of J=0 is forbidden.
The actual
experimental result is shown in Fig. 6, while the fine
splitting is due to the isotopic shift of H35Cl and H37Cl.
EJ = J ( J + 1)
Fig. 5. HCl:
vibrational and rotational transitions, (b)
spectrum lines, (c) intensity distribution.
140
Part B4
III. ELECTRON COLLISIONS WITH
MOLECULES
The interaction time of an e- with a molecule is:
tc ~ 10-16 10-15 s
The typical time for a molecule to vibrate is:
tvib ~ 10-14 10-13 s
The typical time for a molecule to dissociate is:
tdiss ~ tvib ~ 10-14 10-13 s
The typical transition time for electric dipole radiation is:
rad ~ 10-9 10-8 s
The typical time between collision in a low pressure
plasma is
c
These time scales are:
tc << tvib ~ tdiss << rad << c
1. Frank-Condon principle
Since tc << tvib, electronic excitations are indicated
by vertical transitions in Fig. 7 as the interatomic distance
cannot change in the time scale of the excitation. Such a
process is sometimes called a Frank-Condon or adiabatic
transition.
Since rad >> tdiss,, if the energetics permit, the
molecule will dissociate instead of de-exciting to the
ground state.
It should be noted that only certain energies can be
adsorbed which correspond to the spacings indicated;
however, the distribution in interatomic spacing as the
molecules vibrate result in a broadening of the acceptable
excitation energies. Photoelectron excitations occur in a
manner similar to this; however they have an additional
constraint of spin conservation. In electron impact, spin
conservation is not important as the process can be treated
as a three body event. Note that excited states can be
short-lived or may be metastable. Various electronic
levels have the same energy in the unbound limit
( R ).
2. Dissociation
Shown in Fig. 8 are various processes which lead to
dissociation in molecules.
e- + AB ! A + B + eProcesses b-b' result in the excitation to a state in which
141
the excited molecule is not stable. This results in the
production of A+B with the excess energy being
converted into translational energy of the molecular
fragments. Excitations to curve 2 with lower energies
result in a bonded electronically excited state. Excitation
to curve 3 which is repulsive is indicated by processes aa'. These excitation result in the production of A+B.
Excitation c indicates the excitation to an excited state
which is stable. This state can relax by the emission of a
photon to curve 3 resulting in dissociation or by curve
crossing to a repulsive state (curve 4) again resulting in
dissociation. Note in the latter process, B* is produced in
an electronically excited state.
3. Dissociative ionization
Figure 9 are processes associated with ionization
and dissociative ionization.
e- + AB ! AB+ + 2eNote that curve 2 represents a stable molecular ion state
(AB+). This state can undergo dissociative recombination
to produce fast and excited neutral fragments.
e- + AB ! A + B+ + 2eA repulsive ion state, curve 4 is also shown which always
results in fragmentation after ionization.
4. Dissociative recombination
The electron collision illustrated in Fig. 9 as d and d
represents the capture of the electron leading to the
dissociation of the molecule. Thus, this process is called
dissociative recombination.
e- + AB+ ! A + B*
5. Dissociative electron attachment
Depending upon the dissociation energy and the
electron affinity of B, the dissociative electron attachment
can be categorized into autodetachment, dissociative
detachment, electron dissociative attachment, and polar
dissociation:
e- + AB ! ABe- + AB ! AB- ! A + Be- + AB ! A+ + B- + eFigure 10 shows a number of examples of electron
attachment processes for molecules: (a) the excitation to a
repulsive state requires electron energies greater than the
threshold energy, (b) the attachment requires little
electron energy and can result in a stable negative ion or
fragmentation, (c) the capture of a slow electron to a
142
Part B4
repulsive state results in the formation of a negative ion
that is a fragment. (d) the excitation to a neutral excited
state with sufficient energy that a positive and negative
ion are simultaneously formed, i.e., polar dissociation.
6. Electron impact detachment
Electron-negative ion collision can result in the
detachment of the electron to yield a neutral and one
additional electron. Here the electron affinity of the
negative ion plays an important role.
e- + AB- ! AB + e- + e7. Vibrational and rotational excitation
Electrons with sufficient energy can excite
molecules into higher vibrational and rotational energy
levels. This is typically a two-step process, where
electron is first captured (a negative ion forms) and then
detached to generate a vibrationally excited molecule.
e- + AB (v=0) ! ABAB- ! AB (v>0) + eIV. HEAVY PARTICLE COLLISIONS
143
A- + B+ ! A + B*
3. Associative detachment
The associative detachment process is shown in Fig.
12. Depending upon the energy level of AB-, the
dissociation process varies.
A- + B ! AB + e4. Transfer of excitation
As discussed in Atomic Collisions and Spectra,
transfer of excitation can take place in the plasma,
including the Penning ionization.
A + B ! A+ + B + eA + B ! A* + B
A + B* ! A+ + B* + e- (Penning ionization)
A + B* ! AB+ + eA + B* ! A* + B
5. Rearrangement of chemical bonds
Chemical bond rearrangement can also take place in
the plasma, making the composition more complex.
AB+ + CD ! AC+ + BD
AB+ + CD ! ABC+ + D
AB + CD ! AC + BD
AB + CD ! ABC + D
6. Three-body processes
As discussed in Atomic Collisions and Spectra, three
body collisions are important processes that conserve the
energy and momentum, and allow complex chemical
reactions to take place in the plasma gas phase.
a) Electron-ion recombination
e- + A+ ( +e- ) ! A + ( +e- )
b) Electron attachment
e- + A ( +M ) ! A- + ( +M )
c) Association
A+ + B ( +M ) ! AB+ + ( +M )
d) Positive-negative ion recombination
A- + B+ ( +M ) ! AB + ( +M )
144
Part B4
energy. The inelastic scattering produces a host of excited
states, which then relax and/or interact by collision
between particles or by collisions with the walls of the
reactor.
An energy level diagram for oxygen, a diatomic
molecule, is shown in Fig. 13 to illustrate the complexity
of possible gas phase reactions in an oxygen plasma. The
electron states of O2-, O2, and O2+ are shown. Only
attractive states are shown in this simplified energy
diagram, though repulsive state do exist.
Several
attractive states shown here are metastables, including 1g,
1 +
g , and 3u states of O2. The threshold energy for
oxygen excitation processes is shown in Table 1.
A short list of the reactions that take place in an
oxygen plasma is in Table 2 for an analysis: Reactions 1
and 2 involve the inelastic scattering of an electron with
neutrals and are characterized by collision cross-sections,
while reactions 3-5 are heavy particle collisions and are
quantified in terms of rate coefficients.
Table 2. Reactions in an oxygen glow discharge
Eth (eV)
1.95
2) O2+e ! O2(1g) + e
0.98
3) O2+e ! O2(b1g+) + e
1.64
4) O2+e ! O2(A3u+) + e
4.50
5) O2+e ! O2(*) + e
6.00
6) O2+e ! O2(**) + e
8.00
7) O2+e ! O2(***) + e
9.70
8) O2+e ! O2+ + 2 e
12.20
9) O2+e ! O + O + e
6.00
10) O2+e ! O + O
3.60
Reaction
ki
, cm2
1. Ionization: e + O2 ! O2+ + 2e
2.7x10-16
2. Dissociative attachment: e + O2 ! O + O
1.4x10-18
+
-11
3
+
3. Charge transfer: O + O2 ! O2 + O
2x10 cm /s
4. Detachment: O + O ! O2 + e
3x10-10 cm3/s
2.3x10-33 cm6/s2
5. Atom recombination: 2O + O2 ! 2O2
2E
(1)
i ( E ) f ( E )dE
m
o
This equation represents an integration over all electron
energies of the product of the electron velocity, the
collision cross-section, and the electron-energy
distribution function. The collision cross-section can be
considered the probability that during a collision a certain
reaction takes place. It has the units of area to be
dimensionally correct; however, this area has only a vague
interpretation in terms of the distance at which the
particles must approach to react in a specific manner. The
collision cross-section is a function of the energy of the
electron in most cases. The energy dependence for a
number of processes is shown in Fig. 14.
The modeling of an oxygen discharge using MBD is
reasonably successful in predicting rate constants for
inelastic collisions with a threshold energy below that of
the average electron energy. However, for predicting
ki =
145
higher threshold events, such as ionization, such modeling
gives poor results. The failure to model the high energy
processes reflects the greater deviation from MBD in the
high energy tail region, as the Druyvesteyn model
suggests. For the high energy processes, the variation of
collision cross-sections with energy and the effects of the
electron-velocity distribution must be taken into account.
In addition, the power dissipation in a plasma can be
related to the various collisions and their energies,
Power =
where
2m
E km nN + E j k j nN + E ki nN + E kd n
M
j
(2)
e + O2 O2*(A3 u ) + e 2O(3P) + e
1b.
2.
3.
4.
2O + O2 2O2
3O O + O2
O + 2O2 O3 + O2
146
Part B4
4 Fno dn
1
nv + 2k1 < ne > (no n)
=
2
(2no n) dV
2R
Flowrate = F
Cross-section dL = dV
(3)
n
2no n
(4)
7 106 yF
Power V
(5)
147
C
2E
3 -1
B
k = f (E)
; units: k [cm s ]; Te [eV]
( E )dE = ATe exp
0
m
Te
A
2.1810-2
2.3310-11
2.1110-9
9.4710-11
1.0210-10
1.7410-10
2.3510-5
1.5310-9
2.1410-10
6.3510-11
1.0710-8
5.4710-9
3.7010-9
2.0010-7
5.6110-8
5.0910-10
9.2910-9
1.0010-7
1.0010-7
5.4010-10
3.4710-33
5.0010-10
B
-1.433
0.237
0.232
0.445
0.641
0.575
-0.953
0.183
0.189
0.187
0.075
0.073
0.053
-0.235
-0.241
0.457
0.265
0.000
0.000
0.000
0.000
0.000
C
16 304.0
9163.8
54866.0
113840.0
150810.0
48883.0
124040.0
113280.0
126890.0
148090.0
134280.0
141 400.0
146 370.0
126 730.0
143 350.0
155 900.0
47 436.0
0.0
0.0
0.0
-810.0
0.0
Ethreshold
0.07
2.50
9.25
11.48
3.61
9.00
9.55
10.85
12.55
11.65
12.45
12.75
10.85
12.15
13.01
3.55
148
Part B4
Figure 19: Elastic and inelastic collision cross sections as a function of energy for electron
impact reactions of Cl2.
Total Scattering
Total Elastic
10
Single ionization
of Cl
-20
Total Ionization
Neutral
Dissociation
0.1
Total Dissociative
Attachment
0.01
0.01
0.1
10
100
149
Plasma Diagnostics
151
Blue
shading
No
shading
Red
shading
Wavelength
1. Optical Emission
Optical emission from a plasma occurs primarily
through the electron impact excitation of atoms or
molecules to an excited state, followed by a relaxation to a
lower energy state releasing a photon containing an
energy equal to the difference between these two energy
states. Analysis of the photon energy (wavelength of
light) and spectral emission information of species can
therefore be used to infer the composition of the species
that produced it.
Optical emission of atoms is reasonably straightforward, since only electronic state transitions can occur.
Therefore atomic spectra have sharp, nearly monoenergetic, and well-defined peaks corresponding to
transitions between various electronic states.
Molecules, however, have a larger number of
electronic states, and also have both vibrational and
rotational states superimposed upon their electronic states.
The small energy differences between the vibrational and
rotational states, the broadening of emission energies
caused by collisions, and movement of the emitting
molecules cause the emission to overlap and form bands
rather than sharp emission peaks at easily identified
frequencies. Typically, a sharp bandhead is observed and
can be used to identify the band, while red or blue
shadings, as shown in Fig. 1, are due to the fact that the
upper state is less or more tightly bounded than the lower
states. Keep in mind that a bandhead or a shading is not
always observed.
At higher pressures, collisions broaden the emission
energy, but such broadening is not usually observed in the
low pressure discharges used in plasma processing. Other
152
Part B5
E*-E1
Energy
Vib 3
Electronic
0.8-18
6500-145000
Vibrational
0.02-0.6
200-5000
Rotational 0.00001-0.0006
0.1-5
Plasma
Lens
Spectrometer
Detector
Recorder
2. Spectroscopy
Optical emission spectroscopy, which measures the
light emitted from a plasma as a function of wavelength,
time, and location, is the most commonly used plasma
diagnostic probe for microelectronics fabrication
processes. The rate at which such transitions occur is
determined by the quantum mechanical similarity of the
states. This similarity leads to selection rules that indicate
the allowed transitions. The energy of the photons
emitted by the plasma, therefore, is characteristic of the
composition and energy state of species within the
plasma. The spectra can be used to analyze both the
chemical species that make up the plasma and their state
of excitation. Because it is non-intrusive, inexpensive,
and can be easily incorporated into an existing plasma
reactor, it quickly gains popularity in the microelectronics
industry for monitoring the plasma processing. However,
the large information content makes the interpretation of
the spectra difficult. For this reason, it is primarily used
as a fingerprint that is compared with spectra taken
while a process is working well to identify the state or
drift of the plasma. As a research and development tool, it
can be very useful in understanding the basic processes
within the plasma. It can be quite effective and
quantitative if combined with other measurements.
A schematic of the optical emission analysis is
shown in Fig. 3. Optical emission measurements are
usually made through a quartz window on the plasma
reactor, with a monochromator system that measures
emission wavelengths between 200 and 1000 nm by the
rotation of a diffraction grating. A typical scan would
take on the order of a minute for this range of frequencies.
Plasma Diagnostics
White light
Prism
(a) prism
(b) grating
Fig. 4. Spectrometers
153
Therefore, only one emission energy can be monitored as
a function of time during each experimental run in an
etching process. Multichannel optical emission analyzers
are also available, where diode array detectors are used to
collect the spectra from a monochromator with a fixed
grating. This technique has the advantage of acquiring a
scan in a few seconds, so that multiple scans can be made
during a process cycle to characterize transient process
behavior.
The required components for setting up an optical
emission spectroscopy include:
a) Optical window: quartz or sapphire is used to
maximize the transmission of short wavelengths of
light. Experimental difficulties can be caused by
deposition on the chamber window through which
the optical emission is sampled. Such deposits can
selectively absorb emission, altering the spectra that
are observed. In some cases, this can be overcome
by purging the window with the input gas to keep
the window clean. In addition, heating of the optical
windows could also reduce the deposition.
b)
Spectrometers: Most of the photon detectors have a
fairly flat response for different wavelength of the
photon, thus, it is essential to disperse the plasma
emission into the different wavelengths prior to the
photo-detector.
Several most commonly used
spectrometers are listed here:
Prism: A prism works because the refractive index
of glass depends on the wavelength. However, the
use of prism in the plasma spectroscopy is not as
common these days due to its limited resolving
power. Note that the resolving power is defined as
/ and it defines how well a spectrometer can
disperse the light into the different wavelengths.
Gratings: After the invention of the ruling machine
by Rowland, the diffraction gratings have been used
extensively for optical spectroscopy. Gratings with
a resolving power of 100,000 can be easily obtained
in a moderate size grating. For example, an 8 cm
wide grating with 1200 line per mm has a resolving
power of about 100,000 comparable to a glass prism
with a base of 80 cm. One of the few shortcomings
of the gratings is its relatively small optical
throughput when a high resolving power is needed.
Filters: If the wavelength of a particular emission is
known and the interference from the nearby
wavelength can be neglected, one can use filters to
154
Part B5
focusing electrode
dynodes
anode
photocathode
(a) photomultiplier
multi-channel
plate
photocathode
photodiode
phosphor
screen
(b) photodiode
Plasma Diagnostics
155
resolution is usually several KHz.
d) Other optical components: There are many different
optical components such as lens, mirrors, optical
fibers, optical stops, etc., available for various
spectroscopic applications. These components are
used to enhance the overall performance of the
spectroscopic system and should be selected
carefully.
156
Part B5
e + F ! F* + e
If the optical emission originates from the dissociation of
molecular fluorine:
e + F2 ! F + F* + e
OES Intensity
88
.1
:2
Si
OES Intensity
Si
:2
51
.6
nm
nm
Cl
2:
25
5n
m
Cl
:7
Cl 92.4
:8 6
37 nm
.59
nm
Cl
240
Cl2
200
260
280
Wavelength (nm)
+
Cl2
400
300
600
Wavelength (nm)
800
1000
3. Actinometry
To interpret the optical emission spectra (OES) of a
plasma the kinetics of excitation and relaxation must be
considered. The optical system contains emission at a
large number of wavelengths, corresponding to allowed
transitions between a combination of electronic,
vibrational, and rotational states. The electron impact is
responsible for creating the excited neutrals, so the
electron distribution function must be known in order to
calculate quantitatively the concentration of neutrals from
Plasma Diagnostics
157
the measured emission intensity.
To illustrate the analysis, let nA be the concentration
of the free radical A and let I be the optical emission
intensity integrated over the linewidth. The emission due
to excitation from the ground state A can be written as
I = A n A
(1)
with
(2)
158
Part B5
plasma power are varied. The concentration of Ar is
computed using the ideal gas law based on the total
process pressure and the fraction of gas that is used.
Now choose an excited state T* of the trace gas T
that has nearly the same excitation threshold energy,
T * A* * . The cross sections A (v) and 'T (v) for
v3f e(v)
T
/
v
Fig. 14. Principle of actinometry.
I ' = 'T nT
(3)
with
(4)
I
I '
C AT = f k D ( ), Q A* , C A , k D (' ), QT * , C 'T
14.5
14.0
13.5
13.0
2px States
(x=1-10)
12.5
12.0
11.5
1s3
1s5
(Metastable)
1s2
1s4
(Radiative)
Ground state
(5)
(6)
Plasma Diagnostics
159
argon (as shown in Fig. 15) at '=7504 with a threshold
energy of 13.5 eV. Typically, nT is chosen to be 1-5% of
the feed gas density.
Recently, Malyshev and Donnelly developed the
trace rare gases optical emission spectroscopy (TRGOES) as a new, nonintrusive method for determining
electron temperatures (Te) and estimating electron
densities (ne) in low-temperature, low-pressure plasmas,
as shown in Fig. 16. Their method is based on a
comparison of atomic emission intensities from
equimixture of He, Ne, Ar, Kr, and Xe rare gases to the
plasma. For Maxwellian electron energy distribution
functions (EEDF), Te is determined from the best fit of
theory to the experimental measurements. For nonMaxwellian EEDFs, Te is derived from the best fit
describes the high-energy tail of the EEDF.
4. Advantages/disadvantages
The primary advantage of optical emission analysis
is that it is non-intrusive and can be implemented on an
existing apparatus with little or no modification. It
provides spatial and temporal resolution of the plasma
emission spectra and has very large information content
which yields much valuable information about the plasma
if analyzed properly.
Moreover, it is relatively
inexpensive and can be used on more than one reactor.
However, its complex spectrum is often difficult to
interpret. Therefore, typically only the atomic lines are
used in plasma process analysis. Molecular lines of
unknown origin are often used to monitor species whose
emission changes significantly upon the end point in
plasma etching processes. It is reasonably effective as a
trouble-shooting tool to identify contamination as water in
the process or an air leak, as long as the normal
processing spectra haven been recorded. One of the most
limiting factors of OES as a process diagnostic tool is the
maintenance of the optical window. Deposition and/or
etching of the window can significantly modify and
attenuate the OES signal.
5. Application: end-point detection
End point detection is used to determine the end of a
plasma etching process to better control etching fidelity.
The use of single wafer etchers where the process is
terminated after a standard over-etch time determined by
end point detection has resulted in improvement of
reliability and reduced process variation.
The control of the over-etching time is important to
the quality of etching processes. It is necessary to have a
Part B5
Pl
as
Bi ma
as on
on
Bi
as
Pl off
as
m
ao
ff
160
OES Intensity
Cl (837.62nm)
Si (251.67nm)
O (777.42nm)
Cl2 (257.01nm)
500
1000
1500
time (s)
Measuring
Intensity of
light emitted
from discharge
Monitoring
Emission from
reactive
species and/or
etch products
End point
Average for
all wafers
Full Wafer
Interferometry
Intensity of
light
interference
Changes in
film thickness
One wafer
and in situ
etch rate
monitor
Optical
Reflection
Interference
phenomena or
reflectivity
differences
Changes in
film thickness
One wafer
and in situ
etch rate
monitor
Mass
Spectrometry
Gas
composition
Etch products
Average for
all wafers
Plasma Diagnostics
161
162
Part B5
such that the measured optical emission intensity
I = O nO + O2 nO2
has a component proportional to the O2 feed density nO2
as well as the atomic density nO . The actinometric
measurement of nO will fail if O nO O2 nO2 , which is
the case for the 7774 measurement.
Incident
n1
n2
n3
Reflected
b c
film
Laser
/2
(7)
n2 sin 1
interferometry
measures
the
periodic
Plasma Diagnostics
163
(a)
Intensity
1.0
0.8
0.6
0.4
0.2
0.0
0
10
10
Time (min)
(b)
Intensity
1.0
0.8
0.6
0.4
0.2
0.0
0
Time (min)
Fig. 23.
Computed interferometry
signal without photoresist.
The
interference pattern (a) originates from
a more reflective thin film than that in
(b).
(a)
Intensity
0.6
0.4
0.2
0.0
0
1.0
10
10
Time (min)
(b)
Intensity
0.8
0.6
0.4
0.2
0.0
0
Time (min)
164
Part B5
v = 2E / m
(8)
t = L / v = L m / 2Vz
The field created by the quadrupole structure causes the
ions to transverse between the poles in a helical path that
is stable for only a particular mass-to-charge ratio (Fig.
28). The ions that successfully pass through the mass
filter are collected and the resulting current is amplified to
form the mass spectrometer signal. Varying the AC and
DC potentials allows the selection or scanning of mass-tocharge ratios, as shown in Fig. 29.
To avoid detecting species that are modified by
collisions with chamber walls, the mass spectrometer
must be mounted as close to the discharge as possible, so
that the gas entering the mass spectrometer chamber has
minimal opportunity for contacting the walls. In most
plasma processes, the mass spectrometer measures the gas
Plasma Diagnostics
165
composition at a point between the chamber and the
pumping system. However, for research studies, the mass
spectrometer can be built into the system so that it
measures the ion and neutral flux incident upon an
electrode through the use of an orifice in the electrode.
With this technique, both the ion and neutral fluxes upon
the electrode can be recorded, and the species to be
detected pass from the plasma reactor into the ionizer of
the mass spectrometer in a line-of-sight path, minimizing
the corruption of the gas composition caused by collision
of gas with walls.
ZTB CH 3
F rom Zr, C, H , O
Isotope Ca lculatio n
5000
4000
367
3000
360 365 370 375 380 385 390 395 400
m/e (amu)
2000
1000
0
150
200
250
300
350
m/e (amu)
400
166
Part B5
10000
7500
(a) O2/Ar=0
Zr+
5000
ZrO+
2500
ZrO2H+
0
10000
7500
5000
(b) O2/Ar=0.5
100
150
100
50
50
2500
90
94
98
0
10000
160
164
168
(c) O2/Ar=4
7500
ZrO2+
5000
ZrO3H3+
2500
ZrO4H5+
0
90 100 110 120 130 140 150 160 170
Mass-to-charge ratio
"
O, H
"
O
e
e
e
! ZrO3 H 3 ZrO 2 H ZrO Zr
"
O, 2H
(9)
ZrCl2+
ZrCl3+
+
ZrCl4
2
2
167
Radicals
Ions
Transport to Surface
Surface
Diffusion
Desorption of
Volatile
Products
Desorption
Step Growth
Nucleation
and Island
Growth
_ (1)
_
CF4 +e CF2 + 2F +e
(2)
SiF4
(6)
F
SiF4
(3) (4) (5)
F SiFx SiF4
surface
I. PLASMA CHEMISTRY
To characterize plasma-surface interactions, we first
reviewed elementary reactions, gas phase kinetics, and
surface kinetics. Plasma processing shares a relatively
common set of steps, by which the surface reaction proceeds. Ion bombardment can alter the kinetics of one or
more of the steps, creating an enhancement of the etching
or deposition rate; this effect is thought to be the primary
cause of anisotropy in the surface topographical change.
A reasonable set of steps for plasma etching that can be
used to understand the etching mechanisms are as follows
(Figs. 1 and 2):
1. Creation of the reactive species within the plasma
phase by electron-neutral collisions and subsequent
chemical reactions:
e + CF4 CF3 + F + e
2. Transport of the reactive species from the plasma to
the substrate.
3. Adsorption of the reactive species on the surface (either physisorption or chemisorption, Fig. 3).
4. Dissociation of the reactant, formation of chemical
bonds to the surface, and/or diffusion into the substrate with subsequent formation of the desorbing species:
F* + SiFx SiFx+1
5. Desorption of the product species:
SiF4(s) SiF4(g)
6. Transport of the product species into the plasma.
7. Simultaneous re-deposition of etching products.
II. SURFACE REACTIONS
168
Part B6
Ea
KT
ERs = ko e
Cl2
Cl
(1)
Etching
Rate
o
(A/min)
Cl
Time
Q (#/cm2/s)
ko (cm2s/#min)
Poly-Si
61019
Si<100> 2.31019-1.11022
2.5710-14
3.5910-15
Ea {eV}
0.29
0.108
169
silicon substrate can greatly change the spontaneous
etching rate of polysilicon by F and Cl atoms. Houle
studied the etching of Si in the presence of F and showed
that the doping effect in which heavily n-type polysilicon
was etched more rapidly than p-type or undoped, was a
result of the band bending at the surface. The adsorbed
atomic F began negatively ionized by an electron tunneling from the bulk Si. If the field caused by the band
bending aided the transport of F into the surface, the reaction rate is accelerated. As the band bending is a function of the Fermi level, the doping changes the etching
rate.
In Cl etching of Si, the same doping effect occurs,
however, it is more pronounced. Atomic chlorine does
not appreciably etch p-type and undoped polysilicon at
room temperature, however, it etches n+-type polysilicon
spontaneously with one to two order magnitude increase
in etching rate. Ogryzlo termed this effect field enhanced etching, in that the large electron density in the
valence band causes the Fermi level to bend upwards.
This band bending facilitates charge transfer from silicon lattice to the electronegative and chemisorbed Cl atoms, makes the Si-Cl bonding more ionic, allows for more
flexibility in the bonding geometry, and creates more
chemisorption sites. The incorporation of chlorine atoms
is thus enhanced, as well as the etching rate. The slower
etching of Si by Cl and Br than F is probably due to the
larger size of Cl and Br and the greater sterric hindrance
effect.
2. Spontaneous deposition
Deposition of thin films due to reactive radicals
with low volatility is common in both etching and deposition processes. In these reactions, the sticking coefficients
of the free radicals are of critical importance of deposition
kinetics. For example, SiO2 deposition by PECVD is
widely used as the interlayer isolation between metal lines
in MOSFET device, and SiO2 deposition can be done with
different precursor chemistries. Figure 6 shows the conformal deposition of SiO2 over high aspect ratio features
in a TEOS/O2 plasma, due to the small sticking coefficients of the reactants. Figure 7 shows a non-conformal
deposition profile of SiO2 deposited in a silane/O2 plasma,
due to the large sticking coefficient of the reactants.
In etching processes, deposition of reactants or redeposition of etching products can be useful or detrimental, depending upon the process of interest. In the case of
etching of SiO2, a polymer layer formation is thought necessary for the etching, though too thick a polymer layer
170
Part B6
Loading
H2 addition
C2 F4 C4 F10 C2 F6
-200
O2 addition
CF4
Etching
-100
Polymerization
0
1
171
h e-
(displacement
of the lattice)
(possible implantation of the ions)
E
Y ( Eion ) = Cit S n ion
E
it
Ar+
Ar+ (Steinbruchel)
Ar+ (Balooch)
Ar+ (Tachi)
Etching 0.6
Yield
Si
+
Ar 0.4
0.2
0
0
10
15
(2)
0.8
20
25
E ion
30
E
Y ( Eion ) = C it S n ion
E
it
E
f th
E
ion
(3)
E
E
E
1/
S n ion Eion2 , and f ion = 1 th
E
E
E
it
ion
it
1/
1
Y ( E ion ) = A ( E ion2 E th/ 2 )
(4)
(5)
where Eth is the threshold energy and A is a constant depending on the particular ion-target combination. Good
agreement is observed by employing this universal energy
172
Part B6
0.6
0.4
Cl+
Etching
Yield
Si
+
Ion
0.2
Ar+
Cl+ (Barone)
0
0
10
15
E ion
Cl+
Si
dependence of ion bombardment induced etching processes to Ar+ etching of polysilicon, as shown in Fig. 10.
In the case of reactive ion sputtering (chemical
sputtering), reactive ions yield higher etching rate than
that of inert ions due to the formation of volatile species
with the reactive etchant. The sputtering yield of polysilicon by Cl+ is a linear function of the square root of the ion
energy, as shown in Fig. 11, and is much higher than that
by Ar+ ions. The extrapolated threshold energy is approximately 10 eV, which is lower than that measured by
Ar+ sputtering of polysilicon (~35 eV). The reduction in
threshold energy is caused by the formation of a heavily
chlorinated layer that reduces the surface bonding energy
and allows for subsequent incorporation of chlorine into
the silicon lattice (Fig. 12). Good agreement is observed
by comparing the experimentally measured sputtering
yield to molecular dynamic simulation results reported by
Barone and Graves (Fig. 13). They confirmed the square
root ion energy dependence of reactive chlorine ion etching of silicon over the energy range of 10 to 50 eV, and
observed that the etching product stoichiometry depends
strongly on the ion energy. Therefore, in comparison with
the spontaneous etching, higher etching rate is achieved,
as shown in Fig. 14.
In a sputtering process, most of the flux is ejected
by momentum transfer, in which the ion bombarding the
surface collides with individual surface atoms transferring
momentum with each collision. The energetic collision
partners are displaced and also undergo a series of binary
collisions over a time period of about 10-12 seconds.
Etching results when an atom at the surface receives
enough energy that it can break loose from the surface
potential and leave the surface. For a normal incident ion,
at least two collisions are needed for the momentum's direction to be reversed and a surface atom to be sputtered.
For ion bombardment at an angle of 40 or greater off
normal, only one collision is needed for a surface atom to
be dislodged, i.e., sputtered.
As the ion incident angle exceeds 70, the sputtering
yield drops off significantly because the ion tends to reflect from the surface dissipating less energy in the collision cascade. Note that the sputtering yield is defined as
the number of surface atoms removed per incident ion
(Fig. 15). As momentum scales with the square root of
energy, the yield also scales with the square root of the
ion bombardment energy. It also increases with the mass
of the ion. For Ar+, the sputtering yield of Si is 0.5 at 1
keV and peaks at 1.0 at 3 keV. As the ion energy is fur-
173
Normalized yield
ther increased, the cross section for scattering at the surface decreases and the sputtering drops. An ion with a
greater mass dissipates a greater fraction of its momentum
near the surface, increasing the probability that sputtering
Etching
occurs. There is generally a threshold energy for sputterRate
ing which is a few bond strengths associated with the
o
(A/min)
minimum energy it takes an ion to displace a surface atom
and thus can be well correlated with other measurements
+
of surface removal energy such as sublimation energy. A
Cl
typical threshold energy is about 25 eV.
Cl
Because of the angular dependence with the largest
etch yield at approximately 60, surface features with
Time
about that angle etch more rapidly, resulting in surface
Fig. 14. Higher etching rate achieved facets with a specific angle. An ion-bombarded surface
by reactive ions compared to reactive will roughen forming surface peaks or needles that point
neutrals.
toward the ion bombardment angle. Their conformation is
due to this preferential sputtering angle and redeposition
of the sputtered products. If any impurity is present that
5
has a lower etching rate, the impurity will congregate at
the point of the needles. In etching process with a large
4
physical sputtering component, the surfaces roughen as
they etch (formation of grass as shown in Fig. 16), in par3
malize
ticular if carbon, oxide, or some other involatile material
2
is present.
1
Three other mechanisms occur in sputtering: thermal spikes, surface damage, and electronic excitation. In
0
a thermal spike, the energy of the ion is dissipated as heat,
0
30
60
90
resulting in a short-lived (10-8 sec), high-temperature tranIon Incident Angle (degree from
Ion incident angle (degree from normal)
sient located within a short distance of the ion impact.
Fig. 15. Dependence of etching yield on This high temperature induces surface molecules and ation incident angles.
oms to desorb rapidly with a kinetic energy that are in
equilibrium with the thermal spike temperature. This
mechanism is probably not significant for the sputtering
of low vapor pressure materials like metals, but could be
significant in the sputtering of metal compounds that have
higher vapor pressures.
Ion
Electronic excitation occurs due to the tunneling of
bombardment
an electron to neutralize the ion just before it strikes the
Roughened
surface. The excited surface state (that has the energy of
surface
ionization of the incident ion) can relax by the emission of
atoms in some materials. Ions therefore have a slightly
greater sputtering yield than neutrals, but this difference
Fig. 16. Formation of grass due to
micromasking.
can only be observed near the threshold-sputtering yield.
The third sputtering mechanism is the creation of
surface damage that degrades into molecular species after
the collisional event. These molecular species can then
desorb in time and leave with an energy that is characteristic of the bulk temperature of the sample. This can be
Poly
SiO2
174
Part B6
thought of as an ion-induced degradation of the surface.
When a surface is exposed to a flux of reactive neutrals
and ions, it has been shown that an adsorbed layer of reactants can form, resulting in a halide-like surface. Thus,
ion-induced plasma etching may contain similar mechanistic steps.
Sputtering of a compound results in a shift in stoichiometry of the surface, i.e., the surface becomes richer
in the less volatile material. For example, ion bombardment of SiO2 produces a surface that is rich in Si as the O
is more volatile. This enriched layer is thin being of order
of a few monolayers in thickness and increases in thickness with the ion bombardment energy.
Knock-on or atomic mixing also takes place during
ion bombardment. Ions striking surface atoms can drive
those atoms into the lattice several atomic monolayers in
depth. This process is termed knock-on and results in the
mixing of layers as sputtering takes place.
175
176
Part B6
Cl+ and Cl
Etching
Rate
o
(A/min)
Cl+
Cl
Time
Fig. 22.
Ion-enhanced etching increased the etching rate by order(s) of
magnitude.
4
75eV Cl+ and Cl
3
Etching
Yield
Si
+
Cl
0
0
100
200
300
400
Cl
Flux Ratio +
Cl
Fig. 23. Ion enhanced polysilicon etching by Cl atoms with Cl+ ions as a function of ion energy and neutral to ion flux
ratio.
1.5
1
Etching
Yield
Si
+
Cl
0.5
Cl/Cl+=200
0
0
30
60
90
177
Ytotal = C ( ) [Y0 + Yi ]
1.2
= C ( ) [Y0 (1 Cl ) + Cl ]
(6)
where C() is a constant representing the angular dependence, is the ion incident angle, and , the surface cover Si
Cl
age of chlorine, is a function of the neutral to ion flux ra0.4
tio. All three parameters, s, , and Yo, of the model scale
linearly with the square root of ion energy and can be inCl alone with SiCl
corporated into a profile simulator to predict feature evo0
lution in high-density plasma etching processes. A de0
10
20
30
SiCl
Etching
Yield
ion-enhanced etching yield in the presence of Cl+ and in the presence Cl+ and
Cl.
III. LOADING
It is generally observed that in a plasma etching
process the etching rate drops as the etching area exposed
to the plasma increases. This decrease in etching rate is
true for processes that consume a major portion of the reTable 2.
Simplified phenomactive species created in the plasma. Processes that are
enological surface kinetics model for
limited by the surface reaction kinetics do not exhibit this
Cl+ ion-enhanced polysilicon etching
behavior. In processes where a loading effect is observed,
of polysilicon with Cl.
the etching rate is typically proportional to the concentration of the reactant. For the case of etching m wafers with
Cl( g ) + s
Cl( s )
a plasma that produces single etching species, the loading
c (
effect is given as
Cl(+g ) + ) Cl( s )
,c ) Cl
Si( s ) + 4Cl( s ) ( SiCl4( g ) + 4
CF4 /O2
4
3
Ro/ Rm 2
CF3Br/He
1
0
CF3Cl
0
4
6
8
# of wafers
10
Ro
Ak
= 1 + m = 1 + w w
Rm
Ak s
(7)
178
Part B6
Shown in Fig. 27 is a set of curves that demonstrate the
effect of flow rate on etching. It should be noted that if
the utilization is high, it may show up as a lack of dependence on power. At very low flows, a typical process will
respond linearly with flow rate at a given power, with
higher flows, the etching rate of increase will become
slower and go through a maximum. At very high flows,
etching rate decreases, as un-reacted species are carried
away.
Similarly, micro-loading is also observed in the microelectronics fabrication, which refers to the different
etching rate across a wafer when there are densely populated lines and isolated lines coexisting on the wafer, exposing to the plasma. Similar to the well known effect
that the average etch rate depends on how many silicon
wafers that have to be etched, the area of exposed silicon
at a local scale causes the variation in the etching rate, as
shown in Fig. 28. The differences in local pattern density
will make one area of a wafer etch at a different rate than
others, and it is necessary to take these effects into consideration when designing the device layouts.
IV. SELECTIVITY
Plasma is seldom used to etch blanket films in microelectronics fabrication. The etching of photoresist and
the underlying substrate is also important since the etching selectivity is never infinite and aspect ratio dependent
etching often causes some etching of the underlying substrate or thin film.
Using the etching of polysilicon gate as an example,
the etching will result in some etching of photoresist and
Fig. 28. Micro-loading effect.
needs to stop on the thin gate oxide (SiO2). The etching
selectivity between Si and SiO2 measured by 100 eV Ar+
and Cl is approximately 30, as shown in Fig. 29. Higher
4
0.4
selectivities for polysilicon with respect to silicon dioxide
or photoresist are desired for patterning finer features.
3
0.3
Addition of 1% oxygen to a chlorine plasma is found to
Poly
Etching
Etching
reduce the etching rate of silicon dioxide significantly,
Yield
Yield
2
0.2
and increase the selectivity of polysilicon over silicon diSiO
Ar
oxide to 70.
1
0.1
The angular dependence of etching polysilicon difSiO
fers from that of SiO2 with 100 eV Ar+ and Cl, as shown
0
0.0
in Fig. 30. The etching yield measurements are taken at a
0
50
100
150
200
Cl
+
Ar
2
+
179
Poly
tching
Yield
Si
+
Ar
normal. Maximum etching yield at near normal ion incident angles is attributed to the rapid implantation of reactive atoms into the substrate with normally incident ions.
The normally incident ions consequently create mixing of
the absorbed surface atoms into the lattice, induce surface
chlorination, and achieve maximum etching yield at near
normal ion incident angles. However, etching of silicon
dioxide is mainly ion-driven, as chlorine incorporation
into the SiO2 film is limited. Ions physically sputter oxygen and silicon, allow chlorine to react to silicon, and
achieve subsequent slight enhancement in the etching
yield. It is necessary to incorporate proper angular dependence for each material into a profile simulator to
model the surface topography evolution during the plasma
etching processes.
0.2
Etching
Yield
2
0.1 SiO 2
+
Ar
SiO2
0
0
30
60
90
CF3 , CF3
CF2
F, F2
e + CF 4
F, F2
CF3
CF 3 e
C 2F6
CF2
C2F4
F ,F
CF2 e
CF
CF
CF
F2
C+F
C2F2
180
Part B6
1
Relative Rate / Intensity
F emission
Etching rate
20
40
60
O2%
produce F for etching. The optical emission used to support this claim shows a correspondence of the etching rate
with the F emission (schematically shown in Fig 32). The
reduction of emission with high O2 concentrations was
explained in terms of dilution of the plasma.
Flamm developed a simplistic, mechanistic framework to correlate the free radical chemistry of halocarbon/oxidant plasmas. Mechanistically, it offers an easy
way to remember the dominant atomic species which exists in plasma with two or more halogens. This model is
based upon the concept that three types of species exist in
this etching system:
181
processes dominate. In addition, it has been shown that
CF2 is often present in high concentrations because of its
low reaction probability. CF2 is technically not a free
radical, the carbon rehybridizes to fill three orbitals and
while one is completely vacant of electrons. To react, the
carbon must rehybridize, making its sticking probability
for formation of polymer much slower than CF or CF3.
Many papers in the literature have hypothesized that CF2
is the dominant species for oxide etching because it has
such a large concentration. In fact, it has a high concentration because it reacts very slowly! The main polymer
forming species are typically CF3 and CF.
In the past few years, reaction sets for CF4 and other
chemistries have been developed. Although they are not
necessarily complete, they typically are able to identify
and explain trends observed experimentally. Databases
by NIST and others have been compiled and kinetic codes
such as ChemKin III are available in the public domain.
Examples of these results for C2F6 + O2 discharges are
shown in Fig. 33. This result explains the observation that
CF4 is formed in fluorine-carbon containing discharges for
typical process conditions in which the neutral gas temperature is low. At higher neutral gas temperatures, the
formation of CF4 can be avoided. This result is caused by
a combination of thermodynamics which favors the formation of CF4 at lower temperatures and COF2 at high
temperatures, as well as the kinetics of gas and surface
phase reactions in which CFx, O, and F radicals recombine.
183
wo
EPR
Efh
Efv
Es
2. Anisotropy. Its usually desirable to have an anisotropic profile, where the etched feature edges
are close to vertical, to maximize packing density on the chip. The etching anisotropy is defined as the ratio of the vertical dimension
change to the horizontal change:
d
A=
0.5( w wo )
as shown in Fig. 1 and 2. A perfect isotropic
etching would have an anisotropy of 1, while
processes with no horizontal etching have an infinite anisotropy.
3. Selectivity. Defined as the ratio of the etch rate
of one material versus that of another. The selectivity of thin film (f) to photoresist (PR) and
the underlying substrate (s) or another film (Fig.
2).
184
Part B7
s f _ PR =
sf _s =
Ef
EPR
Ef
Es
Note that the etching rate of the thin film has two
components: the horizontal and vertical etching
rates. The selectivity of the material being
etched to the overlying masking photoresist layer
is usually of the most concern, since this impacts
CD and profile control, and the thickness of resist required (thinner photoresist is desired to
adequately resolve smaller feature sizes, so selectivity must increase as geometry shrinks).
4. High etch rate. It is needed to keep the throughput of the system or process module high (usually measured in Angstroms/min). There is usually a tradeoff between etch rate and other parameters, such as selectivity and damage.
5. Etch profile control. Bias in etching processes
is defined as the change in dimension of the
feature being etched caused by the lack of infinite anisotropy, over-etching, and/or resist etching. Other etching anomalies include faceting,
trenching, microtrenching, bowing, and notching, as shown in Fig. 3-7.
6. Damage. Plasma damage is an obvious concern,
especially during gate stack formation, which
will be detailed later in the Epilogue.
185
Thick polymer
deposition
After ashing
Conformal layer
2T
Stringer
T
Initial structure
Thick polymer
deposition
Before ashing
No overetch
186
Part B7
ultimately the device performance. To date, simulation work has given invaluable insight into the surface profile evolution during ion-enhanced plasma
etching, using various techniques such as string algorithm, characteristics method, shock-tracing method,
and direct simulation Monte Carlo (DSMC) method.
Dominant reaction mechanisms incorporated in these
simulators include ion induced etching and ion reflection. More recently, localized surface charging
effects and redeposition on the sidewalls have also
been taken into account.
Commonly observed high-density plasma
etching peculiarities such as bowing, tapering, undercutting, trenching and micro-trenching have been
predicted as different physical or chemical mechanisms are incorporated. However, comparing simulation results to etching profiles can not unambiguously determine the dominant surface phenomena as
the profile evolution is often a function of the difference between several mechanisms, e.g. competition
between etching and deposition processes. The profiles can often be fitted using more than one set of
surface kinetics. Therefore, a comprehensive understanding of the dominant plasma-surface reaction
pathways is needed to develop a general, predictive
profile simulator. The use of beam studies in which
the fluxes are well characterized to measure unambiguously the etching kinetics is valuable in determining the functionality of reactive species at specific,
well-defined etching conditions, which can be generalized to the much more complex plasma environment.
III. MECHANISMS OF PROFILE EVOLUTION
The etching of features is dominated by processes which are dependent upon the feature aspect
ratio, i.e. the feature depth to width, as shown in Fig.
12. The etching rate of smaller features is slower
compared to that of larger features. This is called
Aspect Ratio Dependent Etching (ARDE) or Reactive Ion Etching lag (RIE lag), as shown in Fig. 13.
RIE lag in which features of high aspect ratio
etch more slowly is typically caused by the reduction
of ions or neutrals to the bottom of the feature. This
reduction is a combination of both the reduced view
factor of the higher aspect ratio feature and the
charging within the feature. Lowering the process
pressure makes the sheath more collisionless, thereby
187
_
increasing the ion directionality. The greater ion directionality reduces the dependence of the flux on the
+
ee+
+ e
view factor. Increasing the ion energy also increases
Cl
ethe ion directionality in a high-density, low-pressure
e
+
Cl2
+
- +
plasma. The ion energy dispersion is determined by
e
SiCl2
+
+
the collisions in the presheath. Greater acceleration
+
in the sheath results in an increased directionality.
E
The effect of surface charging on the ion flux to the
sheath
bottom is determined by the aspect ratio of the feature and the ion to electron energy ratio. The greater
mask
the energy ratio, the less charging there is.
Since all of the above mentioned phenomena
SiCl4
scales with the feature aspect ratio, the etching profiles are typically modeled to reduce the number of
Cl
poly-Si
Si + 4Cl SiCl4
experiments that must be performed and to project
the effects to other sized features. As the minimum
SiO2
oxide
line width decreases RIE Lag and Inverse RIE Lag,
in which small features etch more rapidly, become
Fig. 14. Non-ideality in plasma etching: (a) ion
distribution is not uni-directional and (b) more significant. The reduction of RIE lag has
driven the industry to low pressure, high-density
photoresist is etched and re-deposited.
plasma sources.
Here, the important parameters affecting the
evolution of features during etching and deposition
are summarized:
bulk plasma
Cl+
oxide
poly-Si
oxide
188
Part B7
photoresist
poly-Si
oxide
189
bulk
plasma
e-
e-
e-
+ e
e+
Cl+
Cl
Cl2
SiCl2
190
Part B7
-1
0
0
0
0
-4
-2
-2
-2
-2
-3
Mask
b = 0.001
-1
b =
104
7 .5
10
2 .5
115
10
3
2
5 7.5 4 32
1
4
Poly
3
b2 = 0.001
1
b = 104
Si
Oxide
5
1
Cl
PR
Si
Cl
+
+
PR
+
+
Si
191
192
Fig. 26. The orientation of the patterned samples with respect to the beam plane, the SEM
images of the etched sample in Fig. 25, and
the Monte Carlo simulated profiles of (left) an
un-shadowed case, and (right) a shadowed
case. Profiles etched by 35 eV Cl+ and Cl at a
neutral-to-ion flux ratio of 200.
Part B7
sotropic etching of the polysilicon. The reduced Cl
flux on the right side of the trench that was shadowed
caused a slower etching rate resulting in unetched
polysilicon. Since the etching of the polysilicon on
the right side is too high to be just Cl+ sputtering, and
too low if all Cl atoms scattered from the photoresist
contributed to the etching of the right side of the
feature. It is postulated that chlorine atoms recombine each other to form molecular chlorine upon colliding with the photoresist surface. Since the reactivity of molecular chlorine is much lower than that
of atomic chlorine on a highly chlorinated surface,
we expect reduced contribution of the scattered neutrals to the etching of the polysilicon on the right
comer. By carrying out a sensitivity analysis for the
recombination probability of Cl on the photoresist, it
is found that a probability of 0.5 best represented the
measured profile.
To test the Monte Carlo simulator, several test
cases were performed in which a subset of all possible surface processes were allowed to occur, the faceting of resist caused by physical sputtering is
shown in Fig. 27. The photoresist lines were subjected to directional ion bombardment with no redeposition of the sputtered species. The highly directional ion flux produces faceting in which the facet
angle is equal to the angle corresponding to the
maximum sputtering yield. The Monte Carlo simulator captures this peculiar effect with the facet being
formed at 63 from the horizontal.
Plasma etching processes typically include
deposition processes from either the plasma or redeposition of etched products. This deposition passivates the sidewalls preventing undercutting and
modifies the etching profile evolution. The Monte
Carlo simulator can predict deposition profiles under
a variety of conditions. Shown in Fig. 28 are two
sample profiles with an isotropic flux of depositing
species from the gas phase on a trench with a unity
aspect ratio. For low sticking probabilities, the deposition is conformal. However, with unity sticking
probability, highly non-conformal deposition is observed.
Figure 29 also demonstrates that the roughening of surfaces during plasma etching can be simulated; a) shows the profile obtained by sputtering a
planar surface in which the sputter products are not
allowed to redeposit. The surface roughening is
193
caused by the statistical variation of the ion flux and
the variation in sputtering yield with angle (the same
effect which causes faceting). Part b) was obtained
under the same conditions but allowing the products
to redeposit. Though very similar to a), one can see
more order in the small pillar-like structures on the
surface and a greater roughness. Redeposition lowers
the etching rate of the surface slightly. In part c)
deposition from the source plane is included and
grass-like structures are observed. The tips of the
surface features receive a greater deposition flux because of their larger view factor of the plasma while
the valleys are shielded and therefore have a lower
deposition flux. Another mechanism for grass formation involves micromasking of the surface that this
simulator can also model.
V. PLASMA DAMAGE
The exposure of wafers to a plasma causes a
variety of damage to the thin films beneath, as
summarized in Table 1 and 2 at the end of this section. The nature of these damage mechanisms is
varied but are all considered faulty during electrical
testing.
1. Contamination
First, metals sputtered from the electrodes or
walls of the chamber can deposit on the wafer, leading to contamination. This source of damage can be
dealt with by reducing the plasma potential with respect to the chamber surface until it is less than the
sputtering threshold, typically about 15 eV. In highdensity etchers, the self-bias of the plasma potential
is approximately 25 eV, thus the electrode on which
the wafer rests must also be regarded as a possible
source. One solution is to make all the surfaces that
can be sputtered of high purity, non-objectionable
materials; typically anodized aluminum.
Contaminants from the ashing of photoresist, in
particular Na and K can be problematic as they are
mobile ions in oxide and can cause the threshold
voltage shift of MOSFETs. Wet cleans are usually
effective in removing these contaminations. Some
studies have indicated that the exposure of the wafer
to ion bombardment and/or UV results in the incorporation of these alkali metals into oxide making it
difficult to be removed by a short wet clean.
2. Particulates
194
Part B7
The dominant loss process in all microelectronics processing is point defects that are typically
attributable to particulates contamination. The major
mechanisms for particulate contamination in plasma
processes are mechanical abrasion of moving robotic
parts, the flaking of deposited films onto the wafer,
degradation of materials, arcing, and the formation of
particulates in plasma phase.
The formation of particulates by mechanical
abrasion is obviously most readily avoided by
avoiding abrasion and/or keeping any parts that must
come in contact with the backside of the wafer.
Limiting the flow rate of venting gas in the robot has
also been found to reduce the levitation of particulates from the bottom of the chamber. In certain
processes, the rapid pump down of chambers leads to
adiabatic cooling of air and can induce water particulates that in turn deposit on the wafers.
Materials that slowly react with the plasma
products can degrade and produce particulates. In
particular, O-rings that are used in seals, if made of
an incompatible material, can shed particulates after
plasma exposure.
In plasma processes, arcs can occur at sharp
corners because of the high electric fields caused by
the small radius of curvature. The rounding of all
edges (sometimes due to welding) reduces arcing and
associated evaporation of material near the arc, and
subsequent particulate formation.
In etching processes, particulates can be
formed in the gas phase under extreme conditions
and their motions are governed by the sheath dynamics. In PECVD particulate formation in the gas
phase is always a concern. The plasma charges particulates negatively, thereby suspending them. They
undergo transport by thermal gradients, ion wind,
concentration gradient, gas flow, electric field, and
many other forces. These particulates can be eliminated from the wafer region by certain gas flow patterns that overcome the dominating electric fields.
The formation can be curtailed before the particles
grow to a size that is problematic by pulsing the
plasma. In the absence of the plasma, the small particles are sweep out of the reactor with the gas flow.
3. Gate oxide damage photon
Transistor gate oxides can also be damaged by
photons with energies greater than about 10 eV,
195
Ions
+
Electrons
+
PR
+
+
++
++
Metal 1
+ +
Dielectric 1
Field Oxide
Gate
196
Part B7
duce lattice damage and the incorporation of hydrogen and fluorine quite deep into the silicon substrate.
Ion bombardment also produces a large flux of interstitials that can diffuse into the lattice. It has been
observed that pn junction below a depth of about 60
nm are not affected, but shallower junction can exhibit leakage and non-idealities. The incorporation of
carbon into the first few monolayers also occurs and
can increase the resistance. The reduction of ion
bombardment energy in general reduces these effects.
6. Post-etch corrosion
Post-etch corrosion is problematic after aluminum metal etches as aluminum undergoes electrochemical attach. Chlorine left on the wafer surface
after etching is absorbed in a condensed water layer
upon exposure to air forming a thin electrolyte solution on the surface. The corrosion is particular problematic when the aluminum is in contact with a different metals such as TiW which is used as a barrier
layer. The presence of a second metal forms a "battery" which discharges by the corrosion of the aluminum. As the technology evolves, since the new interconnect material, Cu, can not be etched, the challenges are on the etching of low-k materials and their
integration.
197
Residue contamination
Exposure to plasma
Present in etching
or deposition
Usually only in etching due
to reaction by-products remaining on surfaces
Exposure to plasma
Both
Dielectrics and
semiconductors
Bonding disruption
Both
Dielectrics and
semiconductors
Both
Dielectrics
Damage type
Basic cause
Materials affected
All
Table 2 Impact of processing flow and of device and circuit layout (IBM)
Impact category
Processing
flow-passivation
Example
Processing
flow-activation
Processing
flow-cumulative
effects
Layout--EMF
loop effects
Interconnect loops can induce EMFs from timechanging magnetic fields, thereby setting up currents across dielectrics
Layout--edge
effects
199
PRINCIPLES OF PLASMA PROCESSING
EPILOGUE
G ate
CURRENT PROBLEMS IN
SEMICONDUCTOR PROCESSING
200
Epilogue
Interfacial and
Space Charge
k
Orientational
dipole
Ionic
dipole
Electronic
dipole
10-2
102
104
4
4
5-7
100
25
11
22
22
15
EBD (MV/cm)
15
15
10-11
0.5
4
10
15
15
5
EG (eV)
8
6
5
4
4
8
7
7
6
VG
Poly
ZrO2
n+
VD
ID
< 20
SiO2
n+
2. Metal gates
Highly doped polysilicon is used for the gate
metal with SiO2, but migration of the dopant causes a
depleted layer which decreases the gate capacitance,
Figure 4.
Etching ZrO2 has problems with requiring the oxide layer to be even thinner. High-k
undercutting and incomplete removal of a silicate insulators alleviate this problem because they can be
layer below the source and drain contacts.
more compatible with elemental and compound gate
metals. Metal gates would also help eliminate possible reactions between poly-Si and the high-k materi-
p-Si
201
als.
The search for an alternative gate electrode relies largely on the work function analysis of the potential gate material, process compatibility with dielectric deposition and annealing, and thermal and
chemical interface stability with dielectrics. To replace n+ and p+ polysilicon and maintain the scaled
performance for 50 nm CMOS and beyond, metals
and their nitrides, silicides, and oxides, such as Mo,
Hf, MoN, HfN, Pt, Ni, and RuO2, are all being researched as potential gate materials. Of course,
proper etching chemistries have to be identified and
studied to allow the patterning of these electrodes.
Delay (psec)
650
Cu and low-
500
350
250
180
130
100
Generations (nm)
Fig. 7. Gate delay and RC time constant, and their
sum, for new and old gate materials.
1. Copper metallization
To reduce the RC delay, copper is chosen for
its lower resistivity compared to aluminum. Copper
is deposited by electroplating because the process is
cheap and robust. However, copper halides are not
202
Epilogue
The challenges in patterning interlayer dielectrics for copper interconnects can be demonstrated by
the two commonly used dual damascene processes
shown in Figure 9. Metal in small vias is used at the
bottom, where space is at a premium due to the high
packing density of devices. The dielectric material
there is low-k, because R is large. Above that layer,
larger trenches can be used, possibly with SiO2 (in
203
CF3
Parylene
F
C
F
PTFE
204
Epilogue
8
7
6
5
4
3
2
1
0
100
20
Fig. 12.
instability (right) of a-C:F films as a function of F
content. As k drops, weight loss increases.
-8
-8
Log(I) (A/mm2)
-9
-9
-10
-10
a-C:F (59%)
=2.18
-11
-11
-12
-12
-13
-13
SiO2
=4.58
Desirable characteristics
Dielectric constant: k ~ 1 3
Good thermal stability, low expansion
Minimal moisture uptake
Good mechanical strength
Electrical leakage/breakdown similar to SiO2
Less film stress
Good adhesion
Less capping material
CMP compatible
Etching selectivity to nitrides/oxides/oxynitrides
O2 ashing compatible
3. Barrier materials
Titanium, tantalum, and tungsten and/or their
Fig. 13. Leakage current of a-C:F films vs. voltage. nitrides with low resistance are used as diffusion barAs k drops, the leakage current increases.
riers and adhesion promoters between copper and
dielectric. The integration of barrier materials with
Si3N4
metal and ILD is critically important in microelecSiO2
tronics interconnection, especially the chemical and
Si3N4
thermal stabilities at the metal/barrier and barSiO2
Adhesion Layer
rier/ILD interfaces (Fig. 14). Atomic layer deposition has been widely studied recently to allow the
Low-K
deposition of these materials over high aspect ratio
SiO2
features with greater conformality.
-14
-14
-2
-2
-1
-1
0
0
1
1
2
2
Metal Barrier
(Cu) (Ti/TiN)
O 2 + e 2O + e
O2 + e 2O + e
+
e-
e-
e-
+
e-
e+
+
+
Cl 2 + e 2Cl + e
e-
e-
e-
+
e-
e+
+
+
e-
e-
e-
ee-
Resist + O CO 2 + H 2 O
Mask
(photoresist)
Si + 4Cl
SiCl 4
Si
Si
SiO2
SiO2
SiO2
BARC
SiO2
Gate
High-k
Si
205
directly.
Electron scattering and the resultant
proximity effect are the major challenges in ebeam lithography. The SCALPEL (Scattering with
Angular Limitation in Projection Electron-beam Lithography) system developed by Bell Labs, Lucent
Technologies, uses high-energy electrons, projected
through a photomask, to create integrated circuit
features just 30-80 nm wide, overcoming many of the
limitations faced in the current optical lithography
systems due to the available wavelengths of light. In
Fig. 15, an electron beam enters from the left and
impinges on a mask thick enough to scatter them but
not to stop them. Electrons passing through the open
areas suffer minimal scattering and diffraction. An
electromagnetic lens refocuses the electrons onto the
photoresist through a back-plane aperture, placed so
that most of the unscattered electrons but few of the
scattered ones will be transmitted.
A group of semiconductor device and equipment manufacturers has recently announced a joint
agreement aimed at accelerating the development of
SCALPEL technology into a production lithography
solution for building future generations of integrated
circuits.
2. Resist trimming
Another alternative to generate finer features is
to trim the photolithographically patterned features
by an oxygen plasma etching process, as shown in
Fig. 16. In a real process concerning patterning the
gate stack, several etching processes have to be used
because the photoresist is deposited on a layer of
bottom anti-reflective coating (BARC) on a layer of
SiO2, which is used as the hard mask in patterning
the gate polysilicon, as shown in Figure 17. It is
then necessary to use a series of plasma etching processes to (1) trim the photoresist, (2) etch the BARC,
(3) pattern the hard mask, (4) ash the photoresist and
BARC, (5) etch the gate, (6) remove the hard mask,
and (7) etch the gate dielectric. Each process requires a different etch chemistry and an in-depth understanding of the surface chemistry to achieve high
etch rate, greater anisotropy, high selectivity, and less
damage. This demonstrates the complexity of the
process of fabricating nanometer-scale transistors,
and the challenge is to simplify and automate the
process for speed, reliability, and reproducibility.
206
SF6
Epilogue
C4F8
C4F8
SF6
207
In electron shading (Fig. 21), electrons impinge on the insulating photoresist and charge it
negatively. The resultant negative space potential
prevents further electrons from entering the trench.
Only ions reach the trench bottom, causing it to
charge up positively. If this potential is connected to
a gate electrode, current will be driven through the
oxide. The current flows back to ground elsewhere
on the chip to complete the circuit. Note that if the
gate is connected to ground during the etch, no
charge buildup can occur. However, when the etching is complete and the gate is isolated, then it can
Fig. 21. Hashimotos diagram of the electron shading
become charged. Thus, most of the damage occurs
mechanism.
just before or during the overetch period. The
amount of charge available to damage an oxide depends on other charge-collecting areas that are connected to the gate. The antenna ratio is ratio of this
total area to the oxide area and can be of the order of
104. The increase in damage with antenna ratio is
well documented. Special diagnostic wafer have
been developed to measure the probability of damage
in various parts of the wafer.
There has been evidence that low Te can reduce
damage, presumably because all plasma voltages decrease with Te. Pulsed discharges have been studied
for this purpose. In the afterglow plasma after RF
turnoff, Te decays faster than does n, so that there is a
period when etching can be done with a low-Te
plasma. Mechanical filters for fast electrons have
been proposed, as well as the introduction of gases
Fig. 22. Monte-Carlo simulation of ion orbits affected
that absorb them. On the other hand, RIE discharges,
by photoresist charging. In this case, curved orbits
can lead to notching of the trench bottom [Hwang and which normally have higher Te than ICPs, have been
found to cause less damage. Though there have been
Giapis, JVSTB 15, 70 (1997)].
computer simulations (Fig. 22), Hashimotos scenario has not been verified directly, and the primary
mechanism for oxide damage is not well enough understood that curative measures can be taken in a
predictive fashion.
VI. SPECIES CONTROL IN PLASMA
REACTORS
Though plasma reactors are available which can
produce uniformity in density and temperature over a
300-mm substrate, it is more difficult to control the
uniformity of various chemical species impinging on
the wafer. There are two problems: uniformity of the
neutral gas, and the distribution of molecular species.
In processes that consume large quantities of
208
Epilogue
the injected gas, such as deposition of amorphous
silicon onto glass substrates for flat-panel displays,
large-area, small-gap RIE discharges can be used.
The gas is injected uniformly through hundreds of
small holes in one of the capacitor plates. In lowpressure etching with ICPs, however, neutrals cannot
easily be injected into the interior of the plasma. A
dense plasma will ionize neutrals injected from a
showerhead ring around the periphery, leaving the
center depleted of neutrals. This has been observed
by Tynan (Fig. 23).
A more difficult problem is to control, for instance in an argonfluorocarbon discharge, the relative concentrations of CF4, CF3, CF2, CF, F, etc. at
the wafer level. Some degree of control can be obtained by creating an argon plasma in the upper part
of the chamber and then injecting the reactant gas
from a showerhead lower down, where Te has cooled
to a suitable level. In traversing the plasma toward
the center, however, neutrals will be dissociated and
ionized progressively, and the relative concentrations
will vary with radius. Plasmas with electronegative
gases pose further problems. Control of the physical
properties of RF plasma may be at hand, but control
of the chemical properties, perhaps by controlling the
EEDF, is a subject for further development.
1. Verify the conversion factor from KT to eV, as well as the numerical coefficients in the
shortcut formulas for D, fp, and fc. Compute these to three significant figures ( and no
more). [It is important to recognize that all those digits in your computer output are not real
data.]
2. Electron Cyclotron Resonance (ECR) plasma sources usually operate at f = 2.45 GHz,
because the technology of magnetrons to produce this frequency has been well developed for
microwave ovens. These sources operate with = c. What magnetic field does this
correspond to?
3. Calculate the Larmor radius of a singly charged argon ion (A = 40) with 15 eV of
perpendicular energy (Mv2) in the magnetic field you calculated in (2).
4. What is the free-space wavelength of 13.56 MHz radiation? [This is the wavelength in
vacuum, where the wave velocity is c.}
5. A plasma resonance probe measures plasma density by finding a peak in its frequency
response at = p. If the peak is found at 280 MHz, what is the plasma density? [Please
give the right number of significant figures.]
6. What is the ion acoustic speed in a 5-eV helium plasma? [This means that KTe = 5 eV.]
Some of these exercises ask you to derive known results for yourself so that you do not blindly
accept what is given to you by someone else. Please attempt to do this before looking at known
solutions. You will be graded on effort. A copied answer will be quite obvious. Other problems
require you to learn how to use a computer to make graphs.
1. Prove that the neutral density at 20C and 1 mTorr pressure is 3.3 1013 cm-3 for a
monatomic gas.
2. The density at which electron-ion collisions are as frequent as electron-neutral collisions was
given in class as 6.9 109 pmTorrTeV2 cm-3. Plot the fractional ionization F at this crossover
point as a function of Te, where F = n /(n + nn).
3. Plot the crossover density above vs. Te for various pressures p. Choose your scales so that
these plots are as useful as possible for your own future use.
4. Using the collision probabilities given in the course notes, calculate the current density in an
ICP if KTe = 3 eV, p = 10 mTorr of Ar, n = 2 1011 cm-3, and E = 0.5 V/cm. Give units.
5. Calculate the cross-field diffusion coefficient D for electrons in a weakly ionized, 4-eV
plasma in 20 mTorr of Ar, with a dc magnetic field of 500G. Give units.
6. (a) Estimate the mean free path of 60-eV primary electrons in a 3-mTorr argon discharge of
density 1012 cm-3, including collisions with both neutrals and ions. (b) About how far does
such an electron go before it creates an ion?
1. Using collision data given earlier, calculate the skin depth in an unmagnetized ICP reactor
running at 13.56 MHz in 10 mTorr of argon with Te = 4 eV and n = 2 1011 cm-3.
2. An RIE reactor has two identical circular electrodes of radius a, separated by a height h. The
space between them is bounded by a grounded, metallic cylinder of radius a and length h.
Different RF voltages VA, B = VA, B sin( A, Bt ) are applied to the two electrodes. Assuming
that the plasma is a perfect conductor, derive an expression for the space potential Vs as a
function of time. [Hint: Write the electron and ion fluxes to each of the three surfaces as a
function of time, and set the total electron flux equal to the total ion flux. The diagram is a
cylinder of revolution around a vertical axis.]
Vs
VA
VB
Ie
Vp
Ie
(V)
-58.0
-56.0
-54.0
(mA)
-0.68
-0.66
-0.64
(V)
-3.0
-2.0
-1.0
(mA)
0.14
0.29
0.48
-52.0
-50.0
-48.0
-46.0
-44.0
-42.0
-40.0
-38.0
-36.0
-34.0
-32.0
-30.0
-28.0
-26.0
-24.0
-22.0
-20.0
-18.0
-16.0
-14.0
-12.0
-10.0
-8.0
-6.0
-4.0
-0.62
-0.60
-0.58
-0.56
-0.54
-0.52
-0.50
-0.48
-0.46
-0.44
-0.42
-0.40
-0.38
-0.36
-0.34
-0.32
-0.30
-0.28
-0.26
-0.24
-0.23
-0.21
-0.17
-0.10
0.04
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
10.5
10.8
11.0
12.0
14.0
16.0
18.0
20.0
22.0
24.0
26.0
28.0
30.0
0.75
1.12
1.62
2.30
3.24
4.52
6.27
8.66
11.93
16.40
22.51
26.36
28.11
28.29
29.08
30.24
31.02
31.56
31.97
32.34
32.70
33.05
33.36
33.54
In doing the homework, there are some good habits which I hope you will learn:
1. Express multiplication with parentheses like (3)(4) instead of 34 or 34, since these can be
misread. Cross your zs so they dont look like 2s.
2. Do not give more significant figures in the answer than are justified by the data. You can use
one more digit in the data than you need in the answer and then round off at the end. But the
answer cannot be more accurate than the most inaccurate piece of data.
3. Carry out calculations algebraically as far as you can; then put in the numbers at the end.
This saves entering numbers over and over again and prevents round-off errors. For instance, in
the examples that follow, you will notice that some factors cancel in the intermediate steps, so
that in the answer, very few numbers have to be entered.
_____________
1. Verify the conversion factor from KT to eV, as well as the numerical coefficients in the
shortcut formulas for D, fp, and fc.
a)
K Boltzmann = 1.381e23 J / K
T=
e = 1.602e19 C
1.602e 19 C
1.381e 23 J / K
= 11600 K / V
KT
D = 0 2 e
ne
1/ 2
T
= eV
n
1/ 2
3 TeV
= 7.43 10
1/ 2
o
e
1/ 2
9 TeV
m = 7.43 10
8.854 1012
1.602 1019
1/ 2
T
= eV
n
1/ 2
T
m = 7.43 eV
n18
1/ 2
e2
0m
1/ 2
1/ 2
1.60 1019
1
=
n1/ 2
fc =
1 e
1 1602 10 19 BG
.
B=
= 2.80 106 BG Hz = 2.80 BG MHz
2 m
2 0.911 1030 104
2. Electron Cyclotron Resonance (ECR) plasma sources usually operate at f = 2.45 GHz,
because the technology of magnetrons to produce this frequency has been well developed for
microwave ovens. These sources operate with = c. What magnetic field does this
correspond to?
f c = 2.8 106 BG = 2.45 109 , BG =
2.45 109
= 875 G
2.8 106
3. Calculate the Larmor radius of a singly charged argon ion (A = 40) with 15 eV of
perpendicular energy (Mv2) in the magnetic field you calculated in (2).
2
Mv = 15eV=(15)(e) joules
2
v =
1/ 2
30e
30e
, v =
M
M
1/ 2
v
30e
rL = =
c M
M 30 AM H
=
e
eB
1/ 2
(30)(40)(1.67 10-27 )
=
1.60 1019
1
B
104
= 0.040 m = 4.0 cm
875
c
3 108
=
= 22.1 m
f 13.56 106
5. A plasma resonance probe measures plasma density by finding a peak in its frequency
response at = p. If the peak is found at 280 MHz, what is the plasma density?
f p = 9 n12 GHz,
0.28
4
9
n12=
= 9.68 10 , n = 0.97 10
9
cs = (TeV / M )
(5)(1.6 1019 )
=
(4)(1.67 1027 )
1. The following Langmuir probe curve, with the ion current already subtracted, shows a biMaxwellian electron distribution.
100
10
0.1
0.01
-30
-20
-10
0
Probe voltage (V)
10
20
b = h sin , t , eV / KTe .
To find the average s, you would normally have to evaluate an awful integral of the form
ln (1 + e
h sin
)d ,
but there is an approximation you can use when h is large. When sin is >0, the 1 can be
neglected, and when sin is <0, the exponential term can be neglected.
a) Find a numerical value for the normal Vdc in the limit Vb 0.
b). Derive an expression for the sheath drop dc without inserting numbers.
Ec (eV)
1000
100
10
1
KTe (eV)
10
5. Multiple choice questions. Use intuition; calculation not required (nor desired).
1. The plasma frequency fp in a plasma reactor is most likely to be in the range
! 1001000 kHz
! 1100 MHz
! 1001000 MHz
! 1100 GHz
! 0.11 THz
! 1 mm
! 1 cm
!1m
! 10 m
3. The Debye length at n = 4 1010 cm-3 in a plasma reactor with KTe = 4 eV is closest to
! 10 m
!1m
! 1 cm
! 1 mm
! 0.1 mm
4. The cyclotron frequency at 1 kG is closest to
! 3 kHz
! 3 MHz
! 3 GHz
! 3 THz
! 875 Hz
! 1 mm
! 1 cm
!1m
! 1 km
6. All walls of an ICP are grounded, and a dc bias of 100 V is put on a large conducting
substrate. The gas is argon, and KTe = 3 eV. The plasma potential Vs is closest to
! 105 V
! 99V
! 5 V
!0V
! +15 V
7. The ion temperature can be measured by the following ways (check all that apply):
! Gridded energy analyzer ! Single Langmuir probe
! Double Langmuir probe
! Microwave interferometry
! Laser induced fluorescence
8. The plasma density is most accurately measured with
! Microwaves
! OES
! Electron saturation current
! Ion saturation current
! Rogowski coils
9. The Bernstein-Rabinowitz-Laframboise theory of Langmuir probes includes the following
effects (check all that apply):
! Sheath formation ! Ion orbital motion ! Electron orbital motion
! Charge exchange collisions
! Conservation of angular momentum
10. In RF HDPs, special techniques are needed to minimize RF interference with the following
diagnostics (check all that apply):
! Gridded energy analyzer ! Magnetic probe
! Langmuir probe
! Microwave interferometry
! Actinometry
1. Compute to three significant figures the numerical coefficients in the shortcut formulas for
D, fp, and fc.
2. Calculate the Larmor radius of an argon ion (A = 40) with 2 eV of perpendicular energy
(Mv2) in a 100G magnetic field.
3. Electron Cyclotron Resonance (ECR) plasma sources usually operate at f = 2.45 Ghz, because
the technology of magnetrons to produce this frequency has been well developed for microwave
ovens. These sources operate with = c. What magnetic field does this correspond to?
4. What is the free-space wavelength of 2.45 GHz radiation? [This is the wavelength in
vacuum, where the wave velocity is c.}
5. If one were to make an ECR source at 13.56 MHz, what magnetic field would be required?
How does this compare with the earths magnetic field?
1. Prove that the neutral density at 20C and 1 mTorr pressure is 3.3 1013 cm-3 for a
monatomic gas.
2. The density at which electron-ion collisions are as frequent as electron-neutral collisions was
given in class as 6.9 109 pmTorrTeV2 cm-3. Plot the fractional ionization F at this crossover
point as a function of Te, where F = n /(n + nn).
3. Plot the crossover density above vs. Te for various pressures p. Choose your scales so that
these plots are as useful as possible for your own future use.
4. Using the collision probabilities given in the course notes, calculate the parallel diffusion
coefficient for a Maxwellian electron distribution at 4eV in 25 mTorr of A.
5. Add a magnetic field of 250 G to the previous problem and calculate the cross-field diffusion
coefficient D.
6. (a) Estimate the mean free path of 50-eV primary electrons in a 3-mTorr argon discharge of
density 1012 cm-3, including collisions with both neutrals and ions. (b) Also estimate the
ionization mean free path.
1. An atomic chlorine plasma in a 100 G magnetic field has KTe = 2.5 eV and KTi = 0.1 eV.
Would you say this was a weakly magnetized or strongly magnetized plasma, and why?
2. The mobility of argon ions in argon gas is 1.17 106 cm/sec per V/cm, and the electronneutral collision probability was given in the lecture notes. Estimate the ambipolar crossfield diffusion coefficient in a weakly ionized discharge in 50 mTorr of argon and a 600-G
magnetic field with KTi = 0.05 eV and KTe = 2 eV. Hint: write down the units used in each
step, and neglect electron-ion collisions.
3. The density profile in an unmagnetized argon discharge in a cylindrical tube of radius a = 2.5
cm has the form
n = n0 J 0 (Tr ) ,
where J0 is a Bessel function of order 0, T is such that J0(Ta) = 0, and n0 = 1012 cm-3.
Supposing that the diffusion coefficient Da is given to you in cm2/sec, calculate the flux of
plasma reaching the walls (in particles/cm2/sec), expressing the result in terms of Da.
1. What is the skin depth in an unmagnetized ICP reactor running at 2 MHz in 10 mTorr of
argon if Te = 3 eV and n = 1011 cm-3? Hint: use our crossover criterion to see if you have to
include both electron-neutral and electron-ion collisions.
2. An RIE reactor has two identical circular electrodes of radius a, separated by a height h. The
space between them is bounded by a grounded, metallic cylinder of radius a and length h.
Different RF voltages VA, B = VA, B sin( A, Bt ) are applied to the two electrodes. Assuming
that the plasma is a perfect conductor, derive an expression for the space potential Vs as a
function of time.
Vs
VA
VB
Ie
Vp
Ie
(V)
-58.0
-56.0
-54.0
-52.0
-50.0
-48.0
-46.0
-44.0
-42.0
-40.0
-38.0
-36.0
-34.0
-32.0
-30.0
-28.0
-26.0
-24.0
-22.0
-20.0
-18.0
-16.0
-14.0
-12.0
-10.0
-8.0
-6.0
-4.0
(mA)
-0.68
-0.66
-0.64
-0.62
-0.60
-0.58
-0.56
-0.54
-0.52
-0.50
-0.48
-0.46
-0.44
-0.42
-0.40
-0.38
-0.36
-0.34
-0.32
-0.30
-0.28
-0.26
-0.24
-0.23
-0.21
-0.17
-0.10
0.04
(V)
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
10.5
10.8
11.0
12.0
14.0
16.0
18.0
20.0
22.0
24.0
26.0
28.0
30.0
(mA)
0.14
0.29
0.48
0.75
1.12
1.62
2.30
3.24
4.52
6.27
8.66
11.93
16.40
22.51
26.36
28.11
28.29
29.08
30.24
31.02
31.56
31.97
32.34
32.70
33.05
33.36
33.54
1. Derive the expression in Eq. (3-21) for the ambipolar diffusion coefficient Da and show that
the approximation of Eq. (3-23) is true only if De >> Di.
2. Using curves given earlier, estimate the cross-field diffusion coefficient for 3-eV electrons in
a 10-mTorr argon discharge in an 800G magnetic field.
3. A cylindrical discharge 2 cm in radius and 50 cm long is filled with a uniform argon plasma
with n = 1012 cm-3 and KTe = 3 eV, with an ambient pressure of 3 mTorr. The system is
maintained in steady state by RF power that is applied from an external antenna. Using the
graph below, calculate the total loss rate of ion-electron pairs from the plasma.
Ionization probability in argon
1E-07
1E-08
<>
1E-09
1E-10
1E-11
1E-12
1E-13
1E-14
1
10
KTe (eV)
100
4. Calculate the skin depth in a 27.12 MHz ICP discharge in 2 mTorr of argon when the plasma
parameters are n = 2 1011 cm-3 and KTe = 2 eV.
5. Calculate the maximum sheath thickness (Debye plus Child-Langmuir) in an RIE discharge
with n = 1010 cm-3 and KTe = 6 eV, when the applied RF voltage is 600 volts peak-to-peak.
HOMEWORK--ChE 290
due May 8, 1996
1. An argon plasma is created in a 5-cm diam glass tube which is long enough that it can be
considered infinitely long. The plasma diffuses radially by ambipolar diffusion across an 0.1
Tesla magnetic field. The electron temperature is 3 eV, and the neutral pressure is 5 mTorr. The
density profile can be taken to be parabolic of the form
2 2
n = no(1 - r /a ),
where a = 2.5 cm. The density no on axis is unknown
a) Using the cross sections given in class, calculate the rate at which ion-electron pairs
are lost per meter of tube length (in terms of the unknown no). Hint: the ions collide mainly by
charge exchange with neutrals, and the electrons collide with both neutrals and ions.
b) Calculate the average <v>ion for the electrons and from that the number of ionelectron pairs created per meter of tube length.
c) Setting the creation rate equal to the loss rate, calculate the value of no.
2. Calculate the saturation ion current to a probe whose tip measures .010 in diameter and 2mm
long. This is in an argon plasma of density 3 1013 cm-3 and electron temperature 2 eV.
NOTE: Extreme accuracy is not required. You do not have to use a calculator if you are careful
to write down clearly what numbers you are multiplying together or dividing.
A1. An unmagnetized argon plasma has KTe = 4.5 eV and n = 5 1011 cm-3. A DC bias of
800V is applied to a large, flat electrode relative to the plasma.
a) Calculate the total Debye and Child-Langmuir sheath thickness in mm.
b) Calculate the ion and electron fluxes to the electrode in particles/cm2/sec.
A2. A low-pressure, uniform argon plasma in a chamber of volume 6 liters and surface area
2000 cm2 is maintained at Te = 4 eV by an unspecified mechanism. Assuming that the ions reach
the walls at the Bohm velocity and that the ionization probability <v>ion at 4 eV is 10-9 cm3/sec,
calculate what the neutral pressure must be.
A3. Write a short answer to each of the following questions.
a) Why is a plasma needed for etching?
b) Why is a plasma needed for deposition?
c) In an RF discharge, why is the ion energy distribution at a substrate narrower if the
frequency is higher?
d) If one plate of an RIE reactor is at +100V and the other at 100V, the plasma potential is
approximately (A) +101V (B) 99V (C) +1V (D) +99V (E) 1V
e) The simplified form of helicon theory assumes that the ion mass is infinite and the
electron mass is zero. But if the dispersion relation is
2
p
=
k cc 2
1(a). The following Langmuir probe curve, with the ion current already subtracted, shows a biMaxwellian electron distribution. Measure the electron temperatures of the two electron
species.
10.00
1.00
0.10
0.01
-30
-25
-20
-15
-10
-5
Probe voltage (V)
10
1(b). An ion energy analyzer is mounted on a grounded substrate to measure the DC ion
distribution reaching the wafer in a 3-eV plasma. Draw on the diagram the grids you
would insert in the design and tell what voltages you would put on each. If the
distribution has the shape shown, draw a rough sketch of the collector current vs.
analyzer voltage curve that you would expect to find. The voltage scale should be
realistic.
sheath
gridded analyzer
0.05
0.04
f (Ei)
0.03
0.02
0.01
Emin
0.00
0
Emax
20
40
60
80
100
120
140
Ei = eVs (eV)
2. A plasma discharge in a long cylindrical tube has everything constant along the axial (z) and
azimuthal () directions, but the density varies radially. The plasma is so weakly ionized that
collisions between charged particles can be neglected. Let KTe and neutral density nn be
uniform everywhere. The discharge is maintained in steady state by ionization at the rate
nenn<v>ioniz balanced against ambipolar diffusion to the wall with a coefficient Da. We
wish to calculate the radial density profile.
a) Show that the shape of this profile is independent of density.
b) Show that the profile has the shape n(r) = n0J0(kr), where J0 is a Bessel function of
order zero and n0 is the density on axis. Write a formula for k in terms of the symbols
given above.
c) (extra credit) The edge density n(a) is completely specified once nn, Te, and Ti (and
hence k) are specified. But n has to be near 0 at the wall. How is this possible?
Hint 1: The equation of continuity in steady state is
nu = Q, u = Dn / n ,
where Q is the density creation rate per unit volume.
Hint 2: The Laplacian in cylindrical coordinates is 2 f =
1 f 2 f 2 f
+
.
r +
r r r 2 z 2
2J
f) How would you increase the ion energy impinging on the wafer to 200 eV, say, in an ICP?
g) Name two ways to measure the ion temperature in a plasma.
h) What is the main feature that makes ECR and helicon reactors different from ICPs and RIEs?
i) What do ARDE and microloading mean?
j) Why are plasmas used to etch aluminum but not copper?
1. A quartz vacuum chamber is filled with 10mTorr of Cl2 gas, which is completely dissociated
when a plasma is created. An RF field maintains a constant ionization fraction of 1% at an
electron temperature of 3.5 eV. Calculate the Debye length in this plasma.
2. Estimate the energy of ions bombarding the walls of the chamber in the previous problem.
(Hint: use the Bohm sheath criterion, and add the acceleration in the normal sheath. Neglect
any additional sheath drop due to the RF oscillations. )
3. Calculate the ratio of plasma frequency to electron cyclotron frequency in a plasma in a 1.5 T
magnetic field if the plasma density is 5 1018 m-3.
Additional questions for graduate students
4. A Lam TCP etcher operates at 13.56 MHz and produces a plasma density of 8 1011 cm-3 in
the vicinity of the antenna. About how far does the RF field penetrate into the plasma?
5. If the charge-exchange cross section for Ar+ on Ar is 8 10-15 cm2 when KTi = 0.1 eV, how
large, approximately, is the ambipolar diffusion coefficient in a 20-mTorr argon discharge
with KTi = 0.1 eV and KTe = 2 eV?
Chemical Engineering
Principles of Plasma Processing
UCLA, Winter 2000
Due: January 18, 2000
1. The probability of finding a molecule with a particular speed in a low pressure gas follows the
Maxwell-Boltzmann Distribution function:
3
m 2 2
mu 2
p(u ) = 4
u exp
2k BT
2k BT
Show that:
__
(1) the average speed of the gas molecule is: u = up(u )du =
o
8k BT
m
(2) the root-mean-squared speed of the gas molecules is: u rms = u p (u )du
2k B T
(3) the most probable speed of the gas molecules is: u mp =
m
3k B T
m
2. Determine the gas flow regimes and calculate the mean free paths of the oxygen gas molecules
at (1) 1mtorr, 300K and (2) 20 torr, 600K. Assume the characteristic length of the process
chamber is 10 cm.
Chemical Engineering
Principles of Plasma Processing
UCLA, Spring 2002
Due: April 18, 2002
1. The probability of finding a molecule with a particular speed in a low pressure gas follows the
Maxwell-Boltzmann Distribution function:
3
m 2 2
mv 2
p(v) = 4
v exp
2k B T
2k B T
Show that:
__
8k B T
.
m
nv
.
4
40
F (L/s)
30
20
10
0
0
10
20
30
40 50 60
% opening
70
80
90 100
Chemical Engineering
Principles of Plasma Processing
UCLA, Winter 2000
Due: February 3, 2000
1. To use optical spectroscopy to determine the plasma chemistry, you need to determine the
number of photons at various wavelengths accurately. Assume that you have a plasma in that
the electron and neutral density are 2x1011 cm-3 and 2x1013 cm-3, respectively, with the
electron temperature at 3 eV. Use the model shown below to describe the most important
transisions, where Eg, E1, E2, and Ei are ground state, excited state 1, excited state 2, and
ionized state, C1, and C2 are rate of collisional excitation from the ground state (cross-section
of both processes are shown below), and R1g=5x108 s-1, R2g=5x107 s-1, and R21=5x107 s-1 are
rates of spontaneous emission. Calculate the number of photons and their wavelength using
a plasma volume of 100cm3.
Ei
E2
R21
C2
E1
R2g
C1
R1g
Eg
2
1
-15
5x10
-15
cm
1x10
12
25
eV
cm
15
25
eV
2. Determine the ground state levels for Al, Si, P. S. Cl. And Ar. Show how each of the terms
used in the spectroscopic terms of atoms are determined.
3. Determine the rate constant for the reaction: e+O(1D)!O(3P)+e, using the data in Table 8.1
and 8.2. Compare your result to that given in Table 8.2.
Chemical Engineering
Principles of Plasma Processing
UCLA, Spring 2002
Due: April 30, 2002
1. The probability of finding a molecule with a particular speed in a low pressure gas follows the
Maxwell-Boltzmann Distribution function:
3
m 2 2
mv 2
p(v) = 4
v exp
2k B T
2k B T
Show that:
__
8k B T
.
m
nv
.
4
40
F (L/s)
30
20
10
0
0
10
20
30
40 50 60
% opening
70
80
90 100
4. Determine the ground state levels for Al, Si, Cl, Ar, and Br. Show how each of the labels
used in the spectroscopic terms of atoms is determined.
5. Problem 3.9 in the textbook (Lieberman and Lichtenberg)
Chemical Engineering
Principles of Plasma Processing
UCLA, Winter 2000
Due: February 24, 2000
2. Actinometry is widely used in aid the quantification of the optical emission spectra from
plasmas to determine the concentration of various excited species. You have developed an
aluminum etching process using chlorine gas at a pressure of 10mtorr. Your preliminary
experimental results on a pure chlorine plasma indicate that you have a strong emission line
at 837.6 nm. What electronic transition state is this line corresponding to? Which noble gas
and its corresponding emission line will you choose for actinometry and why? With 1 at.%
of the noble gas of your choice mixed in your chlorine plasma, the integrated intensity ratio
of the 837.6nm line to the line of your choice is 15:1. Determine the concentration of
chlorine atoms in your plasma.
If your chlorine plasma is very weakly dissociated, which wavelength(s) of light would you
expect to see with your OES setup? (list two dominant lines for Cl2)
2. Laser interferometry is used to quantify the etching of deposition rate during plasma
processing. You are in charge of etching of 1000nm thick un-doped polysilicon (n=3.88) on
SiO2 (n=1.45) and use a 632.8nm He-Ne laser source to determine the etching rate. Please
determine and plot the interferometry signals as a function of time when you etch (1) unpatterned polysilicon at a rate of 100nm/min, laser incident angle =50o to the normal (2)
photoresist patterned polysilicon with the etching rates of photoresist and polysilicon at
0nm/min and 100nm/min, respectively. Note the photoresist has an index of refraction of 1.6
and the lines are 500nm thick, 500nm in width, and 500nm apart. Use normal incident angle
in this case.
3. Problem 9.3 in LL.
Chemical Engineering
Principles of Plasma Processing
UCLA, Spring 2002
Due: May 21 2002
1. Problem 8.1 in LL.
2. Problem 8. 6 in LL.
3. Use the energy diagram for O2, calculate the wavelength of the photon generated from deexcitation of b1g+ O2 back to its ground state. Assuming that the overall rate of the plasma
ashing process is limited by the following initiation process O2+e!O++O+2e, where the
rate expression is: rO2 = kO2 (Te )ne nO2 . The generated oxygen atoms then diffuse to the
surface and dominate the reaction with the photoresist. Using a perfect continuous stirred
tank reactor model for your plasma reactor, determine the expression for the photoresist
ashing rate at steady state, and sketch how the ashing rate changes with reactor volume,
pressure and electron temperature.
4. Actinometry is widely used in aid the quantification of the optical emission spectra from
plasmas to determine the concentration of various excited species. You have developed an
aluminum etching process using chlorine gas at a pressure of 10mtorr. Your preliminary
experimental results on a pure chlorine plasma indicate that you have a strong emission line
at 837.6 nm. What electronic transition state is this line corresponding to? Which noble gas
and its corresponding emission line will you choose for actinometry and why? With 1 at.%
of the noble gas of your choice mixed in your chlorine plasma, the integrated intensity ratio
of the 837.6nm line to the line of your choice is 10:1. Determine the concentration of
chlorine atoms in your plasma. If your chlorine plasma is very weakly dissociated, which
wavelength(s) of light would you expect to see with your OES setup? (list two dominant
lines for Cl2).
Chemical Engineering
Principles of Plasma Processing
UCLA, Winter 2000
Due: March 14, 2000
1. Estimate the maximum etching rate (nm/min) for physical sputtering of silicon dioxide using
600eV Ar+ (sputtering yield: SiO2 (600eV Ar+) = 1.34). Assume that the ion density at the
sheath edge is 1010 cm-3.
2. CF4 can be used to etch both silicon and silicon dioxide. For the same etch rates and plasma
conditions, SiO2 etching in CF4 plasma exhibits a smaller loading effect than silicon etching.
Assume (a) the etching products are CO2 and SiF4 for SiO2 etching, (b) the etching products are
C2F6 and SiF4 for silicon etching, (c) the recombination probability is zero on the walls, and (d)
the reaction probability of the etchant is unity on the substrates. Show that for a fixed etchant
generation rate and the same loading effect, the SiO2 etch area is four times the silicon etch area.
y
d
w
(a) Assume that dN is the number of precursor molecules incident on a differential width dy
at a sidewall position y due to an isotropic flux emitted from a differential width dx at the
top of the trench. Show that dN is proportional to dxcosx and dycosy, but inversely
proportional to the distance r between the source and sidewall:
cos x cos y dxdy
x
y
dN = A
where cos x = , cos y = , and A is a constant.
r
r
r
(b) Integrating the above equation from x=0 to x=w, and assume a uniform source at the top
y
of the trench. Show that dN/dy 1 cos s , where cos s =
. Note that s is
2
y + w2
the angle subtended by the trench opening as seen at the position y along the sidewall.
(c) Repeat the above mentioned procedure, and determine the non-uniform deposition rate
dN/dx versus x at the bottom of the trench.
Chemical Engineering
Principles of Plasma Processing
UCLA, Winter 2000
Due: March 14, 2000
1. QMS?
2. Problem 9.4 in LL.
3. Estimate the maximum etching rate (nm/min) for physical sputtering of silicon dioxide using
600eV Ar+ (sputtering yield: SiO2 (600eV Ar+) = 1.34). Assume that the ion density at the
sheath edge is 1010 cm-3.
4. CF4 can be used to etch both silicon and silicon dioxide. For the same etch rates and plasma
conditions, SiO2 etching in CF4 plasma exhibits a smaller loading effect than silicon etching.
Assume (a) the etching products are CO2 and SiF4 for SiO2 etching, (b) the etching products are
C2F6 and SiF4 for silicon etching, (c) the recombination probability is zero on the walls, and (d)
the reaction probability of the etchant is unity on the substrates. Show that for a fixed etchant
generation rate and the same loading effect, the SiO2 etch area is four times the silicon etch area.
y
d
w
(d) Assume that dN is the number of precursor molecules incident on a differential width dy
at a sidewall position y due to an isotropic flux emitted from a differential width dx at the
top of the trench. Show that dN is proportional to dxcosx and dycosy, but inversely
proportional to the distance r between the source and sidewall:
cos x cos y dxdy
x
y
dN = A
where cos x = , cos y = , and A is a constant.
r
r
r
(e) Integrating the above equation from x=0 to x=w, and assume a uniform source at the top
y
of the trench. Show that dN/dy 1 cos s , where cos s =
. Note that s is
2
y + w2
the angle subtended by the trench opening as seen at the position y along the sidewall.
Chemical Engineering
Principles of Plasma Processing
UCLA, Winter 2000
4:00-6:00pm, February 10, Thursday, 2000
CLOSED BOOK EXAMINATION
O2
plasma
conductivity for air in a circular tube with a length much greater than its
diameter in the rarefied flow regime is: Ftube = 12.2
D3
, and in the
l
D 4 ( p1 + p 2 )
continuum regime is: Ftube =
, and the valve has a
128l
2
conductance of 50 l/s. To maintain a 0.5 mtorr pressure, at what
gas flow rate should you operate this system (in sccm unit)?
Assume that the gas has the flow characteristics of air. What is the
mean free path of the plasma assuming 100% dissociation
efficiency of oxygen and the reactor is a cube with a dimension of
8 on each side?
valve
pump
(b) In fact oxygen plasma chemistry is quite complex where many reactions occur at various
time scales. Using the energy diagram shown on the next page, (1) depict and explain the
Franck-Condon principle, (2) depict and explain the dissociative ionization reaction, determine
the threshold energy for this reaction, and estimate the energy of dissociated species (note O-O
bond strength is ~5eV), (3) calculate the wavelength of the photon generated from de-excitation
of b1g+ O2 back to its ground state.
(c) Assuming that the overall rate of the plasma ashing process is limited by the following
initiation process O2+e!O++O+2e, where the rate expression is: rO2 = kO2 (Te )ne nO2 . The
generated oxygen atoms then diffuse to the surface and dominate the reaction with the
photoresist. Using a perfect continuous stirred tank reactor model for your plasma reactor,
determine the expression for the photoresist ashing rate at steady state, and sketch how the
ashing rate changes with reactor volume, pressure and electron temperature.
Chemical Engineering
Principles of Plasma Processing
UCLA, Spring 2002
4:00-6:00pm, May 2, Thursday, 2002
OPEN BOOK EXAMINATION
1. Please give a concise answer to the following questions:
(a) Why is a Druyvesteyn distribution a better model for the electron energy distribution than
Maxwell-Boltzman distribution?
(b) What are the differences between Coulomb scattering and polarization scattering?
(c) What is multiplicity?
(d) What are the characteristics of metastables?
(e) Please identify the Ar metastable with the spectroscopic energy state designation and
estimate its ionization energy. (Hint: The ionization energy of Ar is 15.6 eV.)
2. For electron-neutral scattering in a 10 mTorr Ar at 25oC, assume an electron of 4 V is
scattered by a fixed neutral (an elastic hard sphere at rest). Determine the mean free path
and collision frequency using a polarizability of the neutral as: p = 11ao3. (Please
indicate your assumptions clearly).
3. In a plasma, assume that the electron neutral density is 3x1011 cm-3 and the electron
energy distribution function is shown below. Use a simple model where the important
energy states are E0, E1, E2, and Ei, representing the ground state, excited state 1, 2 and
the ionized state. The rate of collisional excitation from the ground state to the excited
state 1 and 2 can be calculated from the cross-sections shown below. The rates of
spontaneous emission are A10=5x108 s-1, A20=1x108 s-1, A21=2x108 s-1. Find the ratio of
species at excited states 1 and 2.
Electron energy distribution function
0.3
Ei
A20
C1
0.1
E0
A21
0.2
E1
C2
E2
A10
0
10
15
20
25
30
E (eV)
1
2
4x10-15 cm2
3x10-15 cm2
15
25
eV
10
15
20
25 eV
Chemical Engineering
Principles of Plasma Processing
UCLA, Winter 2000
3:00-6:00pm, March 22, Wednesday, 2000
OPEN BOOK EXAMINATION
1. Multiple Choices and Short-Answer Questions (3 points each):
(Multiple Choices): point for each correct choice and - point for each wrong choice.
A. What are the selection rules for electron-dipole transition of atoms(a common pathway for deexcitation of excited species in a plasma)?
(a) Change in the orbital angular momentum L = 0
(b) Change in the orbital angular momentum L = l
(c) Change in the spin angular momentum S = 0
(d) Change in the spin angular momentum S = l
(e) Change in the total angular momentum state: J = 0
(f) Change in the total angular momentum state: J = 1
B. What is a metastable in the plasma?
C. Name the major criteria for actinometry to work in quantifying the concentrations of plasma
species.
D. Why is low dielectric material needed for interconnection in microelectronic industry?
(a) Reduce the resistivity
(b) Increase the resistivity
(c) Reduce the capacitance
(d) Increase the capacitance
(e) Reduce the crosstalk
(f) Increase the crosstalk
E. You are in charge of etching of 500nm polysilicon (patterned) on 30 nm silicon dioxide. To
compensate for RIE lag, overetching is required to clear all feature. However, oxide thickness
loss greater than 5 nm during the overetching process is NOT acceptable. You know the plasma
uniformity varies 5% across the wafer, and the polysilicon film thickness varies 5% across the
wafer. What is the minimal selectivity between polysilicon and oxide to ensure less than 5 nm
oxide loss across the wafer?
(a) 10%
(b) 20%
(c) 30%
(d) 40%
F. Explain the reasons for the formation of micro-grass during the etching process and suggest
how it can be eliminated.
G. Ion energy and angular distributions are important to etching patterned features. Which of the
following etching peculiarities can be eliminated if the ion angular distribution is monodirectional (in the direction of surface normal)?
(a) Trenching
(b)
Bowing
(c)
Notching
(d)
Tapering
(e)
Grass
(f)
RIE lag
H. Reactive Ion Etching lag (RIE lag) or aspect ratio dependent etching refers to the etching nonuniformity in plasma etching processes where the small features etch slower than large features.
What are the causes for Inverse RIE lag?
I. Silicon is most widely used in the microelectronic industry. Circle the parameters that affect
the etching rate of silicon in a fluorine plasma.
(a) Substrate temperature
(b) Silicon doping level
(c) Ion incident angle
(d) Recombination of fluorine atoms
(e) Substrate bias
(f) Plasma density
J. You are in charge of etching SiO2 using a CF4/O2 plasma, yet the etching anisotropy is poor.
How could you enhance the etching anisotropy?
(a) Lower the pressure
(b) Increase substrate bias
(c) Increase the substrate temperature
(d) Increase CF4 to O2 ratio
(e) Add F2
(f) Add C2F6
2.(8 points) Surface reaction is a key element in all plasma processes, especially in plasma
etching. Various reactive species compete for available surface sites for adsorption, and sites
are regenerated upon desorption of etching products. Determine the following surface reaction
rate as a function of all the rate constants, NA, and NR if (a) the surface reaction II is rate
limiting (b) the adsorption process III is rate limiting. Plot the reaction rate as a function of NA
for both cases.
A + * 1 A*
(I)
A* 2 R*
(II)
R* 3
(III)
k1
k2
k
k3
R+*
3.(a) (6 points) Oxygen is widely used for ashing photoresist in the microelectronics industry
after the photolithography process. Oxygen atoms are produced by electron impact
dissociation, and the oxygen atoms are consumed in the polymer etching process as detailed
below:
(b) (6 point) Two experiments were performed at 1 Torr where 20 wafers were loaded in the
first experiment (with an average etching rate of 1m/min) and no wafer was loaded in the
second experiment. With the aid of OES, we determined that the atomic oxygen concentration
in the first experiment is 1/5 of the atomic oxygen concentration in the second experiment.
From the model you just developed, estimate the etch rate of the photoresist when 50 wafers
(M=50) are loaded in the reactor.
Chemical Engineering
Principles of Plasma Processing
UCLA, Spring 2002
3:00-6:00pm, June 10, Monday, 2002
OPEN BOOK EXAMINATION
1. Multiple Choices and Short-Answer Questions (4 points each):
(Multiple Choices): 2/3 point for each correct choice and 2/3 point for each wrong choice.
1. What are the selection rules for optical transitions of molecules?
" Change in the orbital angular momentum = 0, l
" Change in the spin angular momentum S = 0, l
" Change in the vibrational state: v = 0
" Change in the vibrational state: v = 1
" Change in the rotational state: J = 0
" Change in the rotational state: J = 1
2. Ion energy and angular distributions are important to etching patterned features. Which of the
following etching peculiarities can be eliminated if the ion angular distribution becomes monodirectional ?
" Tapering
" Grass
" Trenching
" Bowing
" Notching
" RIE lag
3. You are in charge of etching of 600nm polysilicon (patterned) on 10 nm silicon dioxide. To
compensate for RIE lag, overetching is required to clear all feature. However, oxide thickness
loss greater than 2 nm during the overetching process is NOT acceptable. You know the plasma
uniformity varies 2% across the wafer, and the polysilicon film thickness varies 3% across the
wafer. What is the minimal selectivity between polysilicon and oxide to ensure less than 2 nm
oxide loss across the wafer?
"
"
"
"
"
"
10%
20%
30%
40%
50%
60%
4. Why is low dielectric material needed for interconnection in microelectronic industry?
" Reduce the resistivity
" Increase the resistivity
" Reduce the capacitance
" Increase the capacitance
" Reduce the crosstalk
" Increase the crosstalk
5. Which of the following statement(s) in plasma etching is(are) true?
" Spontaneous etching is always small and can be neglected
" Physical sputtering yield scales linearly with the square root of ion energy up to MeV
range
" Physical sputtering yield is independent of the ion incident angle
" Ion enhanced etching is important because the synergism of ions and radicals enhances
the etching rates
" Ion enhanced etching yield is independent of the ion incident angle
" Deposition or re-deposition inside a feature is solely due to the etching of photoresist
material
6. You installed a pump with 200 l/s pumping speed for a plasma reactor of 900 cm3. When 50
sccm O2 is fed into the reactor, what is the mean free path of neutral species if oxygen is fully
dissociated in the discharge?
7. Why is the transition between parahelium and orthohelium prohibited?
8. Name the major criteria for actinometry to work in quantifying the concentrations of plasma
species. Why does mass spectrometry complements the optical emission analysis?
9. Reactive Ion Etching lag (RIE lag) or aspect ratio dependent etching refers to the etching nonuniformity in plasma etching processes where the small features etch slower than large features.
What are the causes for Inverse RIE lag?
2. (15 points) The collision probabilities for electron in He and Ar, and for production of
negative ions by electron impact in O2 are shown qualitatively below. Explain why each
collision probability bears that particular dependency to the electron energy.
He
Pc
Pc
Volts
O2
Ar
Pc
Volts
Volts
3. (12 points) In an oxygen plasma, the electron collisional de-excitation can lead to the
quenching of an excited O* to a ground state O. You know the rate constant for the excitation
process:
e + O (3P) ! O* (1D) + e , k1 = 4x10-9exp (-2.3/Te) cm3/s
Use detailed balancing to determine the rate constant for the de-excitation reaction:
e + O* (1D) ! O (3P) + e
Note, the ionization energy of O*(1D) and O(3P) are 11.6 eV and 13.6 eV, respectively.
4. (18 points) Oxygen is widely used for ashing photoresist in the microelectronics industry after
the photolithography process. Using the energy diagram attached on the next page, (1) depict and
explain the Franck-Condon principle, (2) depict and explain the dissociative ionization reaction,
determine the threshold energy for this reaction, and estimate the energy of dissociated species,
(3) Oxygen atoms are produced by electron impact dissociation, and the oxygen atoms are
consumed in the polymer etching process as detailed below:
(4) Two experiments were performed at 100 mTorr where 5 wafers were loaded in the first
experiment (with an average etching rate of 2m/min) and no wafer was loaded in the second
experiment. With the aid of OES, we determined that the atomic oxygen concentration in the
first experiment is 1/10 of the atomic oxygen concentration in the second experiment. From the
model you just developed, estimate the etch rate of the photoresist when 50 wafers (X=50) are
loaded in the reactor.
5. (19 points) CF4 is widely used in etching Si and SiO2, and its gas chemistry is known to be
quite complex. Consider only the following reactions in a CF4 plasma of ne=1010 cm-3 for F
atom generation, and assume the third body reactions in the high-pressure limit are second order
(independent of the M concentration).
e + CF4 ! CF3 + F + e , k1 = 2x10-9exp(-13/Te) cm3/s
e + CF4 ! CF2 + 2F + e, k2 = 5x10-9exp(-13/Te) cm3/s
F + CF3 +M ! CF4 + M, K3 = 2x10-11 cm3/s
F + CF2 +M ! CF3 + M, K4 = 1x10-11 cm3/s
(1) Let
n F nCF3
nCF4
= A(T ) and
nCF2
nCF3
(2) If the initial concentration of CF4 is no, and all other species concentrations are zero at time =
0, determine the equilibrium concentration of F atoms in terms of no, A, and B.
(3) If the silicon etching is due to F atomic flux only, propose a series of elementary reactions
leading to the etching of silicon.
(4) If the etching rate of silicon scales with the surface F concentration, nFS, in the following
form:
ESi (A/min) = 3x10-12 nFS T1/2 exp(-1250/T).
Determine the silicon initial etching rate for a CF4 pressure of 1 Torr at 300K.